CN1509317A - Thermosetting resin composition and laminates and circuit board substrates made by using same - Google Patents
Thermosetting resin composition and laminates and circuit board substrates made by using same Download PDFInfo
- Publication number
- CN1509317A CN1509317A CNA038002221A CN03800222A CN1509317A CN 1509317 A CN1509317 A CN 1509317A CN A038002221 A CNA038002221 A CN A038002221A CN 03800222 A CN03800222 A CN 03800222A CN 1509317 A CN1509317 A CN 1509317A
- Authority
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- China
- Prior art keywords
- resin
- compositions
- mentioned
- expression
- thermosetting resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920001187 thermosetting polymer Polymers 0.000 title claims abstract description 218
- 239000000758 substrate Substances 0.000 title claims description 46
- 239000011342 resin composition Substances 0.000 title abstract description 3
- 229920001721 polyimide Polymers 0.000 claims abstract description 195
- 239000009719 polyimide resin Substances 0.000 claims abstract description 133
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 122
- 239000003822 epoxy resin Substances 0.000 claims abstract description 119
- 239000004642 Polyimide Substances 0.000 claims abstract description 64
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000002253 acid Substances 0.000 claims abstract description 39
- 150000001875 compounds Chemical class 0.000 claims abstract description 23
- 150000004985 diamines Chemical class 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims description 427
- 239000011347 resin Substances 0.000 claims description 427
- 239000000203 mixture Substances 0.000 claims description 319
- XLJMAIOERFSOGZ-UHFFFAOYSA-M cyanate Chemical compound [O-]C#N XLJMAIOERFSOGZ-UHFFFAOYSA-M 0.000 claims description 138
- 239000004593 Epoxy Substances 0.000 claims description 91
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 79
- 239000011889 copper foil Substances 0.000 claims description 75
- 150000001412 amines Chemical class 0.000 claims description 60
- 238000010438 heat treatment Methods 0.000 claims description 47
- 239000003054 catalyst Substances 0.000 claims description 31
- 125000000962 organic group Chemical group 0.000 claims description 21
- 230000007704 transition Effects 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 10
- 125000003545 alkoxy group Chemical group 0.000 claims description 9
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 8
- NHXVNEDMKGDNPR-UHFFFAOYSA-N zinc;pentane-2,4-dione Chemical group [Zn+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NHXVNEDMKGDNPR-UHFFFAOYSA-N 0.000 claims description 8
- UFKUWSBTKLUIIZ-UHFFFAOYSA-N copper;pentane-2,4-dione Chemical compound [Cu+2].CC(=O)CC(C)=O UFKUWSBTKLUIIZ-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000005843 halogen group Chemical group 0.000 claims description 5
- 230000001737 promoting effect Effects 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 claims description 4
- 229940120693 copper naphthenate Drugs 0.000 claims description 4
- SEVNKWFHTNVOLD-UHFFFAOYSA-L copper;3-(4-ethylcyclohexyl)propanoate;3-(3-ethylcyclopentyl)propanoate Chemical compound [Cu+2].CCC1CCC(CCC([O-])=O)C1.CCC1CCC(CCC([O-])=O)CC1 SEVNKWFHTNVOLD-UHFFFAOYSA-L 0.000 claims description 4
- GEMHFKXPOCTAIP-UHFFFAOYSA-N n,n-dimethyl-n'-phenylcarbamimidoyl chloride Chemical compound CN(C)C(Cl)=NC1=CC=CC=C1 GEMHFKXPOCTAIP-UHFFFAOYSA-N 0.000 claims description 4
- WSFQLUVWDKCYSW-UHFFFAOYSA-M sodium;2-hydroxy-3-morpholin-4-ylpropane-1-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)CC(O)CN1CCOCC1 WSFQLUVWDKCYSW-UHFFFAOYSA-M 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 2
- BZPRATGFHKWAKR-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O BZPRATGFHKWAKR-UHFFFAOYSA-N 0.000 claims 1
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 abstract description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 abstract description 11
- 150000002148 esters Chemical class 0.000 abstract description 4
- 229910000077 silane Inorganic materials 0.000 abstract description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 1
- 210000000988 bone and bone Anatomy 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 138
- 238000000034 method Methods 0.000 description 74
- 230000000052 comparative effect Effects 0.000 description 53
- OJASMMNWWIJWFK-KUSCCAPHSA-N (3r)-1-[[4-[[(3r)-3-(diethylcarbamoyl)piperidin-1-yl]methyl]phenyl]methyl]-n,n-diethylpiperidine-3-carboxamide;dihydrobromide Chemical compound Br.Br.C1[C@H](C(=O)N(CC)CC)CCCN1CC(C=C1)=CC=C1CN1C[C@H](C(=O)N(CC)CC)CCC1 OJASMMNWWIJWFK-KUSCCAPHSA-N 0.000 description 49
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 49
- 239000004567 concrete Substances 0.000 description 44
- -1 polysiloxane Polymers 0.000 description 38
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 37
- 239000010410 layer Substances 0.000 description 36
- 239000011159 matrix material Substances 0.000 description 36
- 229910052751 metal Inorganic materials 0.000 description 35
- 239000002184 metal Substances 0.000 description 35
- 238000004519 manufacturing process Methods 0.000 description 31
- 238000009472 formulation Methods 0.000 description 28
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 26
- 230000015572 biosynthetic process Effects 0.000 description 25
- 239000011888 foil Substances 0.000 description 25
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 229920005575 poly(amic acid) Polymers 0.000 description 24
- 239000002904 solvent Substances 0.000 description 23
- 239000002356 single layer Substances 0.000 description 21
- 229920002799 BoPET Polymers 0.000 description 19
- 239000000047 product Substances 0.000 description 19
- 238000003786 synthesis reaction Methods 0.000 description 19
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 18
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 18
- 230000004927 fusion Effects 0.000 description 18
- 238000003475 lamination Methods 0.000 description 18
- 239000004020 conductor Substances 0.000 description 17
- 239000003960 organic solvent Substances 0.000 description 17
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 16
- 238000001035 drying Methods 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 238000002156 mixing Methods 0.000 description 15
- 239000000126 substance Substances 0.000 description 14
- 239000000178 monomer Substances 0.000 description 13
- 239000001294 propane Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- 238000007766 curtain coating Methods 0.000 description 11
- 230000001771 impaired effect Effects 0.000 description 10
- 229920003986 novolac Polymers 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- YVNRUPSDZZZUQJ-UHFFFAOYSA-N [O].NC1=CC=CC=C1 Chemical compound [O].NC1=CC=CC=C1 YVNRUPSDZZZUQJ-UHFFFAOYSA-N 0.000 description 9
- 235000010290 biphenyl Nutrition 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000004305 biphenyl Substances 0.000 description 8
- CZZYITDELCSZES-UHFFFAOYSA-N diphenylmethane Chemical compound C=1C=CC=CC=1CC1=CC=CC=C1 CZZYITDELCSZES-UHFFFAOYSA-N 0.000 description 8
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 239000012046 mixed solvent Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 150000003457 sulfones Chemical class 0.000 description 8
- ULKLGIFJWFIQFF-UHFFFAOYSA-N 5K8XI641G3 Chemical compound CCC1=NC=C(C)N1 ULKLGIFJWFIQFF-UHFFFAOYSA-N 0.000 description 7
- 206010013786 Dry skin Diseases 0.000 description 7
- 239000012298 atmosphere Substances 0.000 description 7
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 description 7
- 230000006837 decompression Effects 0.000 description 7
- 230000018044 dehydration Effects 0.000 description 7
- 238000006297 dehydration reaction Methods 0.000 description 7
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical class C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 239000004848 polyfunctional curative Substances 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 239000000470 constituent Substances 0.000 description 6
- 239000004643 cyanate ester Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 238000000935 solvent evaporation Methods 0.000 description 6
- 229920006259 thermoplastic polyimide Polymers 0.000 description 6
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 150000002924 oxiranes Chemical class 0.000 description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 5
- 239000002798 polar solvent Substances 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 230000002194 synthesizing effect Effects 0.000 description 5
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N 4-methylimidazole Chemical compound CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 239000004952 Polyamide Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 150000002170 ethers Chemical class 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000007591 painting process Methods 0.000 description 4
- 229920002647 polyamide Polymers 0.000 description 4
- 229920003987 resole Polymers 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 3
- FVCSARBUZVPSQF-UHFFFAOYSA-N 5-(2,4-dioxooxolan-3-yl)-7-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1C(C(OC2=O)=O)C2C(C)=CC1C1C(=O)COC1=O FVCSARBUZVPSQF-UHFFFAOYSA-N 0.000 description 3
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 238000001311 chemical methods and process Methods 0.000 description 3
- BKFAZDGHFACXKY-UHFFFAOYSA-N cobalt(II) bis(acetylacetonate) Chemical compound [Co+2].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O BKFAZDGHFACXKY-UHFFFAOYSA-N 0.000 description 3
- 150000001896 cresols Chemical class 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 125000003700 epoxy group Chemical group 0.000 description 3
- 102000054766 genetic haplotypes Human genes 0.000 description 3
- 150000002576 ketones Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000006798 ring closing metathesis reaction Methods 0.000 description 3
- 238000005728 strengthening Methods 0.000 description 3
- 150000003462 sulfoxides Chemical class 0.000 description 3
- 125000006158 tetracarboxylic acid group Chemical group 0.000 description 3
- 150000003568 thioethers Chemical class 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- MNAHQWDCXOHBHK-UHFFFAOYSA-N 1-phenylpropane-1,1-diol Chemical compound CCC(O)(O)C1=CC=CC=C1 MNAHQWDCXOHBHK-UHFFFAOYSA-N 0.000 description 2
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 2
- ZGDMDBHLKNQPSD-UHFFFAOYSA-N 2-amino-5-(4-amino-3-hydroxyphenyl)phenol Chemical group C1=C(O)C(N)=CC=C1C1=CC=C(N)C(O)=C1 ZGDMDBHLKNQPSD-UHFFFAOYSA-N 0.000 description 2
- BSKHPKMHTQYZBB-UHFFFAOYSA-N 2-methylpyridine Chemical compound CC1=CC=CC=N1 BSKHPKMHTQYZBB-UHFFFAOYSA-N 0.000 description 2
- ILYSAKHOYBPSPC-UHFFFAOYSA-N 2-phenylbenzoic acid Chemical group OC(=O)C1=CC=CC=C1C1=CC=CC=C1 ILYSAKHOYBPSPC-UHFFFAOYSA-N 0.000 description 2
- FUOZJYASZOSONT-UHFFFAOYSA-N 2-propan-2-yl-1h-imidazole Chemical compound CC(C)C1=NC=CN1 FUOZJYASZOSONT-UHFFFAOYSA-N 0.000 description 2
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- FKNQCJSGGFJEIZ-UHFFFAOYSA-N 4-methylpyridine Chemical compound CC1=CC=NC=C1 FKNQCJSGGFJEIZ-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- KXDAEFPNCMNJSK-UHFFFAOYSA-N Benzamide Chemical compound NC(=O)C1=CC=CC=C1 KXDAEFPNCMNJSK-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- 150000008065 acid anhydrides Chemical class 0.000 description 2
- 239000004844 aliphatic epoxy resin Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 125000006159 dianhydride group Chemical group 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 239000004845 glycidylamine epoxy resin Substances 0.000 description 2
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 description 2
- AWJUIBRHMBBTKR-UHFFFAOYSA-N isoquinoline Chemical compound C1=NC=CC2=CC=CC=C21 AWJUIBRHMBBTKR-UHFFFAOYSA-N 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000005060 rubber Substances 0.000 description 2
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 125000005591 trimellitate group Chemical group 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- YKNMIGJJXKBHJE-UHFFFAOYSA-N (3-aminophenyl)-(4-aminophenyl)methanone Chemical compound C1=CC(N)=CC=C1C(=O)C1=CC=CC(N)=C1 YKNMIGJJXKBHJE-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0313—Organic insulating material
- H05K1/0353—Organic insulating material consisting of two or more materials, e.g. two or more polymers, polymer + filler, + reinforcement
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/01—Dielectrics
- H05K2201/0137—Materials
- H05K2201/0154—Polyimide
Abstract
A thermosetting resin composition of the present invention includes (A) a polyimide resin, and as thermosetting components, at least one of (B) a multifunctional cynate ester and (C) an epoxy resin. The (A) polyimide resin is soluble polyimide obtained by reacting, with diamines, acid dianhydride including an ether bond. As (B) the multifunctional cynate esters, a compound having a specific structure, and/or an oligomer thereof is used. As (C) the epoxy resin, an epoxy resin having a dicyclopentadiene bone structure and/or an alkoxy-group-including silane denatured epoxy resin is preferably used.
Description
Technical field
The present invention relates to polyimide resin with (A), (B) multi-functional cyanate (also comprising oligopolymer) and (C) at least a kind of conduct in the Resins, epoxy must composition, and the compositions of thermosetting resin of all characteristic goods such as its dielectric characteristics, thermotolerance, cohesiveness; The laminated product and the circuit substrate that adopt said composition to constitute.Above-mentioned compositions of thermosetting resin is applicable to, as laminated materials such as flexible printing wiring substrate (FPC) and harness substrate etc. and so on, requires the manufacturing of the laminated product of dielectric characteristics, thermotolerance, good cohesiveness etc.
Background technology
In recent years, in the circuit that in various e-machines and electric machine, uses,, make the signal high frequencyization of transmission in order to improve the information processing capability of these machines.In above-mentioned various machines, circuit is to form the wiring substrate (circuit substrate) that distribution constitutes on various substrates, as such wiring substrate, for example, can enumerate flexible printing wiring substrate (also claiming FPC), and multilayer printed wiring board, and harness substrate (combinational circuit substrate) etc.
In above-mentioned wiring substrate, be accompanied by the high frequencyization of signal, the problem of bringing is that in the electric reliability that keeps distribution, the signal velocity that also must suppress circuit descends and the loss of signal.As the matrix material (resin material) that forms circuit substrate, require it to show the dielectric characteristics of low-k and low-dielectric loss tangent in GHz wave band zone here.
Before this, as above-mentioned matrix material, adopt to show good processibility and close-burning epoxies matrix material and thermoplastic polyimide class matrix material.
Wherein, the epoxies matrix material has good processibility and cohesiveness, but dielectric characteristics is insufficient.Concrete is that the epoxies matrix material can be pasted each other at low-temp low-pressure following bonding object (adherend), and also good with the cohesiveness of adherend.Yet, for the epoxy resin matrix material after solidifying since at the specific inductivity of GHz wave band more than 4 and 4, tangent of the dielectric loss angle is more than 0.02 and 0.02, so, descend and loss strengthens in the signal velocity of GHz wave band.
On the other hand, thermoplastic polyimide class matrix material, its dielectric characteristics and excellent heat resistance, but processibility is insufficient.Concrete is, because thermoplastic polyimide class matrix material has characteristics such as thermal expansion is little, heat decomposition temperature height, so, excellent heat resistance.In addition, thermoplastic polyimide class matrix material, below 3.5 and 3.5, dielectric loss tangent is lower than 0.02 at the specific inductivity of GHz wave band, and dielectric characteristics is also good.Yet,, must under high temperature, condition of high voltage, paste processing for bonding in addition each other clung body.
Therefore, the matrix material (matrix material that is called fusion) that fusion Resins, epoxy and thermoplastic polyimide resin obtain is proposed recently, (open day: on February 9th, 1993) reach, (2) Japan openly speciallys permit communique " spy opens the 2000-109645 communique ", and (open day: on April 18th, 2000) disclosed technology was representative as openly specially permit communique " spy opens flat 5-32726 communique " with (1) Japan.
In the communique of above-mentioned (1), disclose a kind of polyimide resin and Resins, epoxy of making and reacted the resin combination that obtains with polysiloxane block, in the communique of above-mentioned (2), a kind of resin combination that is made of specific polyimide resin and Resins, epoxy is disclosed.Adopt the matrix material of these fusion, make the good dielectric characteristics of bringing into play good processibility of above-mentioned Resins, epoxy and polyimide resin simultaneously become possibility, the balance of all characteristics such as cohesiveness, thermotolerance, processibility is better than matrix material in the past.
Yet, adopt the matrix material of above-mentioned fusion, because blending epoxy, make the dielectric characteristics of polyimide resin that the tendency of decline be arranged.Concrete, as mentioned above, adopt the matrix material of fusion, though the balance of all characteristics is good, dielectric characteristicies such as specific inductivity, tangent of the dielectric loss angle are also insufficient, particularly for the high frequency characteristics of GHz wave band, depend on that purposes is insufficient sometimes.For example, with the disclosed resin combination of above-mentioned (1) communique during, even also reach high value more than 3.4 and 3.4 at the specific inductivity that records under the lower frequency of 50Hz as matrix material.For the resin combination of this high-k, can't bear use in the GHz zone.Therefore, in the matrix material of fusion, wish that certainly dielectric characteristics improves more.
July 24 calendar year 2001) therefore, recently, as the trial that improves above-mentioned dielectric characteristics, the scheme of proposition is, for example, (3) Japan openly speciallyyed permit communique " spy opens the 2001-200157 communique " (open day: disclosed technology such as.
In the communique of above-mentioned (3), the resin combination that mixing polyimide resin and cyanate obtain is disclosed.Adopt this technology, because all balance of properties of the matrix material of fusion are good, so also can in purposes such as harness substrate, use effectively.
Yet even in the technology of above-mentioned (3), the problem of generation is that the matrix material of fusion is insufficient to the cohesiveness of the conductor metal that forms distribution (for example, copper etc.).Concrete is for example to adopt pressure cooker testing (hereinafter to be referred as the PCT test), the cohesiveness deterioration of matrix material.
The present invention carries out in view of above-mentioned problem, its purpose is to provide a kind of polyimide resin that contains as necessary composition, and in its all rerum natura, at least at the dielectric characteristics of GHz wave band, processibility, excellent heat resistance, and the cohesiveness after the cohesiveness, particularly PCT test (below be called anti-PCT) is also good, be suitable for making the compositions of thermosetting resin of various wiring substrates and laminated product and the circuit substrate that adopts said composition to constitute.
The content of invention
The inventor is in view of found that above-mentioned problem concentrates one's attention on to inquire into, by the kind of handle as the polyimide resin of principal constituent, the kind of thermoset such as cyanate and Resins, epoxy composition, their use level transfers to suitable degree, can obtain in all rerum naturas, at least remove dielectric characteristics, processibility, outside the excellent heat resistance, and, relevant cohesiveness, anti-PCT is also good, and in resulting compositions of thermosetting resin, even improve processibility and thermotolerance, solidify the back in the specific inductivity of GHz wave band and tangent of the dielectric loss angle also low than original resin combination, and then, the resin combination that cohesiveness and anti-PCT are also good than original resin combination.So finished the present invention.
That is, in order to solve above-mentioned problem, this compositions of thermosetting resin of the present invention contains (A) polyimide resin and epoxy resin at least 1 side conduct must composition as (B) multi-functional cyanate of thermoset composition and (C).
As above-mentioned (A) polyimide resin, can adopt at least, make with following general formula (1):
(in the formula, V represents to be selected from-O-,-CO-,-the divalent group of O-T-O-and COO-T-OCO-, T represents the divalent organic group)
The soluble polyimide that at least a kind of acid dianhydride of expression and the reaction of two amines obtain, at least a kind of two amine that above-mentioned two amines preferably use following general formula (4) to represent:
(in the formula, Y
1And Y
2Respectively independently expression-C (=O)-,-SO
2-,-O-,-S-,-(CH
2)
m-,-NHCO-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=O) O-or singly-bound (Direct Bonding), R
1, R
2And R
3Represent the alkyl of hydrogen atom, Halogen gene or carbonatoms 1～5 respectively independently, m and n represent 1～5 integer); In addition, above-mentioned two amines, more preferably two amines of representing with following general formula (5):
(in the formula, Y
3And Y
4Respectively independently expression-C (=O)-,-SO
2-,-O-,-S-,-(CH
2)
m-,-NHCO-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=O) O-or singly-bound (Direct Bonding), R
4, R
5And R
6Represent the alkyl of hydrogen atom, Halogen group or carbonatoms 1～4 respectively independently, m and n represent 1～5 integer).In addition, as above-mentioned two amines more preferably, comprise at least a kind of diamines with hydroxyl and/or carboxyl.
In addition, in acid dianhydride with above-mentioned general formula (1) expression, the T in this general formula (1), preferably, with being shown in following group (2):
The organic group of expression, or to be shown in following general formula (3):
(in the formula, Z is for being selected from-C
QH
2Q-,-C (=O)-,-SO
2-,-O-and-divalent group of S-, Q is 1～5 integer).
The organic group of expression.
In addition, in this compositions of thermosetting resin of the present invention, be preferred person below 250 ℃ and 250 ℃ as the second-order transition temperature of the used soluble polyimide of (A) polyimide resin.
In addition, in this compositions of thermosetting resin of the present invention, as above-mentioned (B) multi-functional cyanate, preferably from being shown in following general formula (6):
(in the formula, R
7Be selected from have singly-bound, the divalent organic group of at least a kind of aromatic nucleus, aliphatics ring ,-CH
2-,-C (CH
3)
2-,-C (CF
3)
2-,-CH (CH
3)-,-CH (CF
3)-,-SO
2-,-S-,-O-, R
8, R
9Both can be identical also can be different, be selected from-H ,-CH
3,-CF
3, o represents 0～7 integer, p, q are identical or different respectively, the integer of expression 0～3).
The multi-functional cyanate selected in the compound of expression, and/or at least a kind of from its oligopolymer, selecting, more preferably, above-mentioned (B) multi-functional cyanate is to be shown in following group (7):
(in the formula, r and t represent 0～5 integer).
That selects in the compound of expression is at least a.
In addition, in the compositions of thermosetting resin that the present invention relates to, as above-mentioned (C) epoxy resin, preferably adopt to be selected from the Resins, epoxy of representing with following general formula (8), (9) and (10) and/or at least a kind of Resins, epoxy in the silane-modified epoxy resin that contains alkoxyl group:
(above-mentioned G in various is to be shown in following structural
The organic group of expression, i, j, k independently represent 0～5 integer, R respectively
10, R
11, R
12, R
13The alkyl of representing hydrogen atom or carbonatoms 1～4 respectively independently).
In this compositions of thermosetting resin of the present invention, the gross weight of whole compositions of (A) polyimide resin is decided to be C
A, the total amount of whole compositions of (B) multi-functional cyanate is decided to be C
B, the gross weight of whole compositions of (C) Resins, epoxy is decided to be C
CThe time, according to the rerum natura that purpose requires, these ratio of mixture or various ratio of components are stipulated that it is preferred satisfying one of following condition person at least:
C
A∶C
B＝20∶80～90∶10
C
A∶C
B＝95∶5～85∶15
C
A∶C
C＝50∶50～99∶1
C
A/(C
A+C
B+C
C)＝0.5～0.96
C
B/(C
A+C
B+C
C)＝0.02～0.48
C
C/(C
A+C
B+C
C)＝0.002～0.48
In this compositions of thermosetting resin of the present invention, can also contain (A) polyimide resin, (B) multi-functional cyanate and (C) epoxy resin composition in addition, for example, the multi-functional cyanate solidified of promotion (B) curing catalysts can be contained, and in (C) epoxy resin solidified solidifying agent at least a kind can be promoted.At this moment, as promoting above-mentioned (B) multi-functional cyanate solidified curing catalysts, preferably be selected from least a kind in zinc acetylacetonate (II), zinc naphthenate, acetylacetone cobalt (II), acetylacetone cobalt (III), cobalt naphthenate, acetylacetone copper (II), the copper naphthenate.In addition, can also contain promotion (C) epoxy resin solidified solidifying agent and promoting and (C) curing catalyst of Resins, epoxy reaction.
In addition, adopt this compositions of thermosetting resin of the present invention, under 200 ℃～250 ℃ temperature condition, heat it is solidified after, at least it is preferred satisfying a kind of person of following condition: condition 1, specific inductivity below 3.0 and 3.0, dielectric loss tangent is below 0.01 and 0.01; Condition 2, before and after PCT handles, any all at 5N/cm with more than the 5N/cm with the cohesive force of Copper Foil.In addition, in above-mentioned condition 1, specific inductivity below 3.2 and 3.2, tangent of the dielectric loss angle is being more preferably below 0.012 and 0.012.
In addition, this compositions of thermosetting resin of the present invention, contain (A) polyimide resin, with as (B) multi-functional cyanate of thermoset composition and (C) at least a kind in the epoxy resin, and as described (B) multi-functional cyanate, the multi-functional cyanate that use is selected from above-mentioned compound with general formula (6) expression, and/or at least a kind of from its oligopolymer, selecting; As above-mentioned (C) epoxy resin, also can adopt from reaching the Resins, epoxy of (10) expression and/or contain at least a kind of Resins, epoxy selecting the silane-modified epoxy resin of alkoxyl group with above-mentioned general formula (8), (9).
Laminated product of the present invention is the laminated product with the layer that contains described compositions of thermosetting resin more than 1 layer and 1 layer, and circuit substrate of the present invention is the circuit substrate that adopts described compositions of thermosetting resin to constitute.
According to above-mentioned formation, in compositions of thermosetting resin of the present invention, contain above-mentioned (A) polyimide resin as principal constituent, contain as (B) multi-functional cyanate of thermoset composition and (C) at least a kind of epoxy resin.Therefore, adopt this compositions of thermosetting resin, can be fully and also balance bring into play the rerum natura of principal constituent and the rerum natura of thermoset composition well.
Therefore, compositions of thermosetting resin of the present invention is low in specific inductivity, the dielectric loss tangent of GHz wave band, and processibility and thermotolerance are also good, and, cohesiveness, the better composition of particularly anti-PCT.Consequently, compositions of thermosetting resin of the present invention is suitable for circuit substrates such as flexible wiring substrate (FPC) and harness substrate, and the laminated product that uses in these circuit substrates manufacturings etc.
Other purposes of the present invention, feature and advantage can fully be understood by following explanation.In addition, benefit of the present invention also is open-and-shut by following explanation.
The preferred plan that carries out an invention
Being described in detail as follows of one embodiment of the invention.But the present invention is not limited to this.
Compositions of thermosetting resin of the present invention contains (A) polyimide resin as principal constituent, also contains as (B) multi-functional cyanate ester resin (monomer and/or oligopolymer) of thermoset composition and (C) at least a kind in the Resins, epoxy.In addition, laminated product of the present invention and circuit substrate are to adopt above-mentioned compositions of thermosetting resin to constitute.
＜(A) polyimide resin 〉
(A) polyimide resin used to the present invention is not particularly limited, and still, the polyimide resin of solubility (below be called soluble polyimide) is preferred.When adopting soluble polyimide,, needn't handle for a long time so that imidization at high temperature cooperating as (B) multi-functional cyanate of thermoset composition and (C) behind at least a kind in the Resins, epoxy.Therefore, can improve the processibility of resulting compositions of thermosetting resin, be preferred.
" solubility " of so-called polyimide resin, be meant from dioxolane, diox, tetrahydrofuran (THF), N, dinethylformamide, N, at least a kind of solvent selecting in N-N,N-DIMETHYLACETAMIDE, the N-N-methyl-2-2-pyrrolidone N-is (for ease of explanation, be called " solubility judgement solvent ") in, temperature in room temperature～100 ℃ is dissolved 1 quality % and the above person of 1 quality %.The what is called here " room temperature " is meant 10～35 ℃ temperature range.
(A) polyimide resin that uses among the present invention can adopt known method manufacturing.The parent material polyamic acid that concrete is polyimide is to adopt method chemistry or that heat to make imidization manufacturing.
＜acid dianhydride 〉
In the present invention, as the acid dianhydride that constitutes described polyamic acid raw material, concrete is not particularly limited, and still, in order finally to obtain the polyimide of solubility, preferably adopts to be shown at least a kind of acid dianhydride of following general formula (1) expression:
(in the formula, V represents to be selected from-O-,-CO-,-the divalent group of one group of O-T-O-and COO-T-OCO-, T represents the divalent organic group).As the acid dianhydride that is shown in general formula (1), both can only use a kind of compound arbitrarily, also can be that use the compound combination back more than 2 kinds and 2 kinds.
If adopt acid dianhydride with above-mentioned general formula (1) expression, can improve for above-mentioned solubility and judge the solvability of solvent and thermotolerance etc., simultaneously, also obtain easily with as (B) the multi-functional cyanate of thermoset composition and (C) soluble polyimide of the intermiscibility of epoxy resin.
In acid dianhydride with above-mentioned general formula (1) expression, the divalent organic group that the T in this formula represents, preferably to be shown in following group (2):
The organic group of expression, or with the organic group of following general formula (3) expression:
(in the formula, Z is selected from-C
QH
2Q-,-C (=O)-,-SO
2-,-O-and-divalent group of S-, Q is 1～5 integer).
As above-mentioned acid dianhydride, if adopt with at least a kind of organic group that contains the aromatic nucleus that is selected from above-mentioned group (2) and general formula (3), as the acid dianhydride of organic radical because of T, then in resulting soluble polyimide, can obtain, particularly specific inductivity, the dielectric loss tangent at the GHz wave band is low, dielectric characteristics is good, and the also good soluble polyimide of thermotolerance.
As acid dianhydride with above-mentioned general formula (1) expression, particularly from being that good point of balance or the point that is easy to get are considered to the solvability of above-mentioned suitable solvents, all characteristics such as intermiscibility, dielectric characteristics and thermotolerance to the thermoset composition, most preferably adopt to be shown in 4 of following general formula, 4 '-(4,4 '-isopropylidene, two phenoxy groups) two O-phthalic acid dianhydrides:
Perhaps,,, adopt 2 from considering with above-mentioned same viewpoint as acid dianhydride with above-mentioned general formula (1) expression, two (4-hydroxy phenyl) the propane dibenzoates-3 of 2-, 3 ', 4,4 '-tetracarboxylic dianhydride also is preferred.
Self-evident, in the present invention,, have with the acid dianhydride of above-mentioned general formula (1) expression acid dianhydride and also can adopt with outer structure as acid dianhydride.But preferably, the acid dianhydride of above-mentioned general formula (1) expression will reach in whole acid dianhydride composition (full acid dianhydride composition) that polyamic acid uses in synthetic 50 moles and 50 moles more than the %.As long as adopt the acid dianhydride of above-mentioned general formula (1) expression as mentioned above like that, so in the soluble polyimide that obtains, owing to solvability, all good, so be preferred to the intermiscibility and the dielectric characteristics of thermoset composition.
As with the acid dianhydride (other acid dianhydrides) beyond the acid dianhydride of above-mentioned general formula (1) expression, be not particularly limited, but concrete, for example can enumerate trimelitic dianhydride, 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydride, 3,3 ', 4,4 '-sulfobenzide tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic acid dianhydride, 2,3,6,7-naphthalene tetracarboxylic acid dianhydride, 4,4 '-hydroxyl diphthalic anhydrides, 3,3 ', 4,4 '-dimethyl diphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furans tetracarboxylic dianhydride, 4,4 '-two (3, the 4-di carboxyl phenyloxy) diphenylprop acid dianhydride, 4,4 '-hexafluoro isopropylidene diphthalic anhydrides, 3,3 ', 4,4 '-biphenyl tetracarboxylic dianhydride, 2,3,3 ', 4 '-phenylbenzene tetracarboxylic dianhydride, right-benzene diphthalic anhydrides etc.These acid dianhydrides both can be only with a kind, also can be more than 2 kinds and 2 kinds with in addition appropriate combination use of ratio arbitrarily.
＜two amines 〉
In the present invention, as two amines (diamine compound) that constitute above-mentioned polyamic acid raw material, there is not concrete special qualification, but, in order finally to obtain soluble polyimide, preferably adopt at least a kind of two amine (being called for simplicity, " main two amines " in the following description) with following general formula (4) expression:
(in the formula, Y
1And Y
2Respectively independently expression-C (=O)-,-SO
2-,-O-,-S-,-(CH
2)
m-,-NHCO-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=O) O-or singly-bound (Direct Bonding), R
1, R
2And R
3Independently represent hydrogen atom, Halogen group or carbonatoms 1～5, preferred 1～4 alkyl respectively, m and n represent 1～5 integer).As two amines (main two amines) with above-mentioned general formula (4) expression, both can only use a kind of compound arbitrarily, also can use the combination of the compound more than 2 kinds and 2 kinds back.In addition, the Y in above-mentioned general formula (4)
1The expression divalent group or singly-bound, in repeating unit, both can distinguish identical also can be different.
As long as use above-mentioned master's two amines, in the soluble polyimide that finally obtains, when promptly can make it to judge that for above-mentioned solubility the solvability of solvent and thermotolerance are all excellent, also can reduce water-absorbent.
As above-mentioned master's two amines; be not particularly limited; but it is concrete; for example; can enumerate two [4-(3-amino-benzene oxygen) phenyl] methane; two [4-(4-amino-benzene oxygen) phenyl] methane; 1; two [4-(3-amino-benzene oxygen) phenyl] ethane of 1-; 1; two [4-(4-amino-benzene oxygen) phenyl] ethane of 1-; 1; two [4-(3-amino-benzene oxygen) phenyl] ethane of 2-; 1; 2-is two] 4-(4-amino-benzene oxygen) phenyl] ethane; 2; two [4-(3-amino-benzene oxygen) phenyl] propane of 2-; 2; two [4-(4-amino-benzene oxygen) phenyl] propane of 2-; 2; two [4-(3-amino-benzene oxygen) phenyl] butane of 2-; 2; two [3-(3-amino-benzene oxygen) phenyl]-1 of 2-; 1; 1; 3; 3; the 3-HFC-236fa; 2; two [4-(4-amino-benzene oxygen) phenyl]-1 of 2-; 1; 1; 3; 3; the 3-HFC-236fa; 1; two (3-amino-benzene oxygen) benzene of 3-; 1; two (3-amino-benzene oxygen) benzene of 4-; 1; 4 '-two (4-amino-benzene oxygen) benzene; 4; 4 '-two (4-amino-benzene oxygen) biphenyl; two [4-(3-amino-benzene oxygen) phenyl] ketone; two [4-(4-amino-benzene oxygen) phenyl] ketone; two [4-(3-amino-benzene oxygen) phenyl] thioether; two [4-(4-amino-benzene oxygen) phenyl] thioether; two [4-(3-amino-benzene oxygen) phenyl] sulfone; two [4-(4-amino-benzene oxygen) phenyl] sulfone; two [4-(3-amino-benzene oxygen) phenyl] ether; two [4-(4-amino-benzene oxygen) phenyl] ether; 1; two [4-(3-amino-benzene oxygen) benzoyl] benzene of 4-; 1; two [4-(3-amino-benzene oxygen) benzoyl] benzene of 3-; 4; 4 '-two [3-(4-amino-benzene oxygen) benzoyl] diphenyl ether; 4; 4 '-two [3-(3-amino-benzene oxygen) benzoyl] diphenyl ether; 4; 4 '-two [4-(4-amino-α; α-Er Jiajibianji) phenoxy group] benzophenone; 4; 4 '-two [4-(4-amino-α; α-Er Jiajibianji) phenoxy group] phenylbenzene base sulfone; two [4-{4-(4-amino-benzene oxygen) phenoxy group } phenyl] sulfone; 1; two [the 4-(4-amino-benzene oxygen)-α of 4-; α-Er Jiajibianji] benzene; 1; two [4-(4-amino-benzene oxygen)-α, α-Er Jiajibianji] benzene of 3-etc.
As above-mentioned master's two amines, amino two amines (in the following description, for simplicity, being called " master two amines ") are arranged is preferred in the position between particularly.That is, as master's two amines with above-mentioned general formula (4) expression, more preferably adopt be shown in following general formula (5) expression between main two amines:
(in the formula, Y
3And Y
4Respectively independently expression-C (=O)-,-SO
2-,-O-,-S-,-(CH
2)
m-,-NHCO-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=O) O-or singly-bound (Direct Bonding), R
4, R
5And R
6Independently represent the alkyl of hydrogen atom, Halogen group or carbonatoms 1～4 respectively, m and n represent 1～5 integer).If adopt this master two amine synthesizing polyamides acid, there is the occasion of amino master's two amines to compare with adopting contraposition, the solvability of the soluble polyimide that finally obtains is better.
As above-mentioned master's two amines; though be not particularly limited; but it is concrete; for example; can enumerate 1; two [4-(3-amino-benzene oxygen) phenyl] ethane of 1-; 1; two [4-(3-amino-benzene oxygen) phenyl] ethane of 2-; 2; two [4-(3-amino-benzene oxygen) phenyl] propane of 2-; 2; two [4-(3-amino-benzene oxygen) phenyl] butane of 2-; 2; two [3-(3-amino-benzene oxygen) phenyl]-1,1,1 of 2-; 3; 3, the 3-HFC-236fa; 1, two (3-amino-benzene oxygen) benzene of 3-; 1; two (3-amino-benzene oxygen) benzene of 4-; two [4-(3-amino-benzene oxygen) phenyl] ketone; two [4-(3-amino-benzene oxygen) phenyl] thioether; two [4-(3-amino-benzene oxygen) phenyl] sulfone; two [4-(3-amino-benzene oxygen) phenyl] ether; 1; two [4-(3-amino-benzene oxygen) benzoyl] benzene of 4-; 1, two [4-(3-amino-benzene oxygen) benzoyl] benzene of 3-; 4,4 '-two [3-(3-amino-benzene oxygen) benzoyl] diphenyl ether etc.
As above-mentioned master's two amines or a master two amines, especially, adopt 1, two (3-amino-benzene oxygen) benzene of 3-are particularly preferred.If adopt 1, two (3-amino-benzene oxygen) the benzene synthesizing polyamides acid of 3-in the compositions of thermosetting resin that contains soluble polyimide that finally obtains, can obtain solvability, solder heat resistance, the good composition of anti-PCT to various organic solvents.
In addition, as above-mentioned two amines that use among the present invention, except that main two amines, preferably adopt to have hydroxyl and at least a two amines (for simplicity, in following explanation, being called the subordinate diamines) of carboxyl.When two used amines have above-mentioned hydroxyl and/or carboxyl, hydroxyl and/or carboxyl in the soluble polyimide that finally obtains, have been imported.
This soluble polyimide is owing to contain hydroxyl and/or carboxyl, so can become to making as the multi-functional cyanate of thermoset composition (B) and/or (C) epoxy resin solidified catalyzer or curing catalyst.The result is that employing subordinate two amines are solidified into possibility as the compositions of thermosetting resin that contains soluble polyimide of raw material at low temperature or short period of time.
In addition, as (B) multi-functional cyanate of thermoset composition and/or (C) epoxy resin and since may with hydroxyl and/or carboxyl reaction, so, adopt subordinate two amines to make the soluble polyimide of raw material, carry out the crosslinked possibility that becomes by Resins, epoxy etc.The result is can give better thermotolerance, scolding tin thermotolerance and anti-PCT to compositions of thermosetting resin.
As above-mentioned subordinate two amines, get final product so long as contain the diamine compound of hydroxyl and/or carboxyl, and be not particularly limited, but concrete, for example, can enumerate 2, diamino phenols such as 4-diaminophenol; 3,3 '-diamino-4,4 '-dihydroxybiphenyl, 4,4 '-diamino-3,3 '-dihydroxybiphenyl, 4,4 '-diamino-2,2 '-dihydroxybiphenyl, 4,4 '-diamino-2,2 ', 5, xenol compounds such as 5 '-tetrahydroxybiphenyl; 3,3 '-diamino-4,4 '-dihydroxyl ditan, 4,4 '-diamino-3,3 '-dihydroxyl ditan, 4,4 '-diamino-2,2 '-dihydroxyl ditan, 2, two [the 3-amino-4-hydroxy phenyl] propane, 2 of 2-, two [the 4-amino-3-hydroxy base] propane, 2 of 2-, two [the 3-amino-4-hydroxy phenyl] HFC-236fa, 4 of 2-, 4 '-diamino-2,2 ', 5, hydroxyl hexichol paraffinic such as hydroxy diphenyl methane such as 5 '-tetrahydroxy ditan; 3,3 '-diamino-4,4 '-dihydroxydiphenyl ether, 4,4 '-diamino-3,3 '-dihydroxydiphenyl ether, 4,4 '-diamino-2,2 '-dihydroxydiphenyl ether, 4,4 '-diamino-2,2 ', 5, hydroxy diphenyl ether compounds such as 5 '-tetrahydroxy diphenyl ether; 3,3 '-diamino-4,4 '-dihydroxy-diphenyl sulfone (ス Le Off オ Application), 4,4 '-diamino-3,3 '-dihydroxy-diphenyl sulfone, 4,4 '-diamino-2,2 '-dihydroxy-diphenyl sulfone, 4,4 '-diamino-2,2 ' 5, diphenyl sulfone compounds such as 5 '-tetrahydroxy sulfobenzide; 2, two [(hydroxy phenyl) phenyl] alkane compound classes such as two [4-(the 4-amino-3-hydroxy oxygen base) phenyl] propane of 2-; Two (hydroxyphenoxy) biphenol compound classes such as 4,4 '-two (4-amino-3-hydroxy oxygen base) biphenyl; 2, two [(hydroxyphenoxy) phenyl] sulphones 3 such as two [4-(the 4-amino-3-hydroxy oxygen base) phenyl] sulfones of 2-, diamino benzoic acids such as 5-diamino M-nitro benzoic acid; 3,3 '-diamino-4,4 '-dicarboxylate biphenyl, 4,4 '-diamino-3,3 '-dicarboxylate biphenyl, 4,4 '-diamino-2,2 '-dicarboxylate biphenyl, 4,4 '-diamino-2,2 ', 5, carboxyl biphenyl compounds such as 5 '-tetracarboxylic biphenyl; 3,3 '-diamino-4,4 '-dicarboxyl ditan, 4,4 '-diamino-3,3 '-dihydroxyl ditan, 4,4 '-diamino-2,2 '-dihydroxyl ditan, 2, two [4-amino-3-carboxyl phenyl] propane, 2 of 2-, 2-pair [3-amino-4-carboxyl phenyl) hexafluoro] propane, 4,4 '-diamino-2,2 ', 5, carboxyl phenylbenzene paraffinics such as carboxyl diphenylmethyl alkanes such as 5 '-tetracarboxylic ditan; 3,3 '-diamino-4,4 '-dicarboxyl diphenyl ether, 4,4 '-diamino-3,3 '-dicarboxyl diphenyl ether, 4,4 '-diamino-2,2 '-dicarboxyl diphenyl ether, 4,4 '-diamino-2,2 ', 5, carboxyl diphenyl ether compounds such as 5 '-tetracarboxylic diphenyl ether; 3,3 '-diamino-4,4 '-dicarboxyl sulfobenzide, 4,4 '-diamino-3,3 '-dicarboxyl sulfobenzide, 4,4 '-diamino-2,2 '-dicarboxyl sulfobenzide, 4,4 '-diamino-2,2 ', 5, diphenyl sulfone compounds such as 5 '-tetracarboxylic sulfobenzide; 2, two [(carboxyl phenyl) phenyl] paraffin compound classes such as two [4-(4-amino-3-carboxyl phenoxy group) benzene] propane of 2-; Two (hydroxyphenoxy) biphenol compound classes such as 4,4 '-two (4-amino-3-hydroxy oxygen base) biphenyl; 2, two [(carboxyl phenoxy group) phenyl] sulphones such as two [4-(4-amino-3-carboxyl phenoxy group) phenyl] sulfones of 2-; Deng.
In the present invention, above-mentioned master's two amines and above-mentioned subordinate two amines are also with being preferred, still, particularly as above-mentioned subordinate two amines, adopt with following structural represent 3,3 '-dihydroxyl-4,4 '-benzidine (4,4 '-dihydroxyl-3,3 '-dihydroxybiphenyl) is particularly preferred:
Adopt above-mentionedly 3,3 '-dihydroxyl-4 is during 4 '-benzidine synthesizing polyamides acid (finally being soluble polyimide), owing to give good scolding tin thermotolerance and anti-PCT to compositions of thermosetting resin, so be preferred.
In above-mentioned master's two amines and above-mentioned subordinate two amines and time spent, in whole two amines (complete two amine components) that in polyamic acid is synthetic, use, so that main two amines in 60～99 moles of % scopes, subordinate two amines (particularly 3,3 '-dihydroxyl-4,4 '-benzidine) be preferred in 40～1 moles of % scopes and when using.Adopting these 2 kinds of diamines time-likes, when the use range of various two amines departed from above-mentioned scope, rerum naturas such as the solvability of resulting soluble polyimide or compositions of thermosetting resin, scolding tin thermotolerance, anti-PCT had impaired tendency in whole two amine components.
In addition, in the present invention, when synthesizing polyamides acid (soluble polyimide), also can use above-mentioned two amines (being called for simplicity, " other two amines " in the following description) in addition.
As other two amines, though be not particularly limited, but, concrete can enumerate, for example, mphenylenediamine, O-Phenylene Diamine, Ursol D, between aminobenzyl amine, PAB amine, two (3-aminophenyl) thioether, (3-aminophenyl) (4-aminophenyl) thioether, two (4-aminophenyl) thioether, two (3-aminophenyl) sulfoxide, (3-aminophenyl) (4-aminophenyl) sulfoxide, two (3-aminophenyl) sulfone, (3-aminophenyl) (4-aminophenyl) sulfone, two (4-aminophenyl) sulfone, 3,4 '-diaminobenzophenone, 4,4 '-diaminobenzophenone, 3,3 '-diaminodiphenyl-methane, 3,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl-methane, 4,4 '-diaminodiphenyl oxide, 3,3 '-diaminodiphenyl oxide, 3,4 '-diaminodiphenyl oxide, two [4-(3-amino-benzene oxygen) phenyl] sulfoxide, two [4-(amino-benzene oxygen) phenyl] sulfoxide etc.
Consumption to above-mentioned other two amines is not particularly limited, but at the soluble polyimide that finally obtains and contain in its compositions of thermosetting resin, consider that from the viewpoint of avoiding all rerum naturas to reduce in complete two amine components, the user is preferred in the scope that is lower than 10 moles of %.
The polymerization of＜polyamic acid 〉
In the present invention, as (A) polyimide resin that is principal constituent, adopt to be more preferably with above-mentioned raw materials synthetic soluble polyimide, but, this soluble polyimide can promptly make the parent with corresponding construction to polyamic acid by dehydration ring closure (carrying out imidization).Here, be above-mentioned acid dianhydride and two amines as the polyamic acid of parent, react and polymerization (synthesizing) with essence first-class mole.
The polyreaction of polyamic acid, concrete is not particularly limited, and still, when being illustrated in proper order with representational polyreaction, at first, making the two amines dissolving more than a kind and a kind or disperses (diffusion) in organic polar solvent.Whereby, can obtain two amine aqueous solutions.Then,, whereby, make these monomers carry out polymerization, obtain polyamic acid solution the acid dianhydride of this two amine aqueous solutions interpolation more than a kind and a kind.
Above-mentioned each monomeric interpolation is not particularly limited in proper order, both can be added into acid dianhydride earlier in the organic polar solvent, add diamines then, also can be added into two amines in the organic polar solvent in right amount earlier, after adding the acid dianhydride of excess quantity then, interpolation is equivalent to two excessive amines again.In addition, also have oneself various addition meanss of knowing of practitioner.Also have, the what is called here " dissolving " comprises that not only solute is dissolved in the situation in the solvent fully, and, also comprise solute homodisperse or diffusion and situation of being in and dissolving identical state in fact in solvent.
As used organic polar solvent in the above-mentioned polyamic acid polyreaction, be not particularly limited, for example, concrete can enumerate sulfoxide kind solvents such as dimethyl sulfoxide (DMSO), diethyl sulfoxide; N, dinethylformamide, N, benzamide type solvents such as N-diethylformamide; N,N-dimethylacetamide, N, ethanamide solvents such as N-diethyl acetamide; Pyrrolidone kind solvents such as N-N-methyl-2-2-pyrrolidone N-; Phenol, neighbour-,-or phenol solvent such as p-Cresol, xylenol, halogenated phenol, catechol; Hexamethylphosphoramide; Gamma-butyrolactone; Deng.In addition, as required, except that above-mentioned organic polar solvent, also can be used in combination aromatic hydrocarbon such as dimethylbenzene or toluene.
The imidization of＜polyamic acid 〉
In the present invention, as the soluble polyimide that (A) polyimide resin preferably uses, be the above-mentioned polyamic acid solution that obtains to be carried out dehydration ring closure (carrying out imidization) by heating or chemical process obtain.
Concrete grammar to above-mentioned imidization is not particularly limited, and when adopting heating means, can adopt the thermal treatment polyamic acid solution and dehydration method, and when adopting chemical process, can adopt dewatering agent to carry out dehydration method.In addition, under reduced pressure heat and the method for carrying out imidization also can adopt.As the soluble polyimide that adopts among the present invention, when adopting above-mentioned any method to carry out imidization, compare with the parent polyamic acid, the imidization person more than 95% and 95% is preferred.If adopt the soluble polyimide of 95% and 95% above imidization, then can obtain all rerum naturas such as excellent dielectric characteristic (low-dielectric), anti-PCT and thermotolerance.Below, the method for each imidization is illustrated.
At first,, can enumerate, and when carrying out imidization reaction, make the method for solvent evaporation by the above-mentioned polyamic acid solution of heat treated as one of hot method example.By adopting this method, can obtain the soluble polyimide of solid form.Condition during to the employing aforesaid method is not particularly limited, in the present embodiment, and heating condition, for example, in the temperature below 300 ℃ and 300 ℃, the condition of carrying out heat treated in about 5～200 minutes time range is preferred.
Secondly,, can enumerate the dewatering agent that adds in the above-mentioned polyamic acid solution more than the chemical theory amount and catalyzer and carry out dehydration ring closure and react, make the method for organic solvent evaporation simultaneously as one of chemical process example.By adopting this method, can obtain the solid polyimide resin.Condition during to the employing aforesaid method is not particularly limited, but above-mentioned dewatering agent, catalyzer, the heating condition when carrying out the dehydration ring closure reaction, the heating condition when making organic solvent evaporation, in the present embodiment, for example, it is preferred adopting following various condition.
As above-mentioned dewatering agent, for example, can enumerate aromatic anhydrides such as fatty acid anhydride, st-yrax acid anhydrides such as acetic anhydride etc.In addition, as above-mentioned catalyzer, for example, can enumerate aliphatic tertiary amines such as triethylamine; Aromatic tertiary amines such as xylidine; Hetero ring type tertiary amines such as pyridine, α-picoline, β-picoline, γ-picoline, isoquinoline 99.9; Deng.Heating condition when carrying out the dehydration ring closure reaction is preferred in the temperature below 100 ℃ and 100 ℃, and the heating condition when making organic solvent evaporation is preferred in the temperature below 200 ℃ and 200 ℃, in about 5～120 minutes time range.
Here, (A) of the present invention in order to obtain polyimide resin needn't make solvent evaporation when adopting above-mentioned hot method or chemical method, also can obtain polyimide resin.In this method, owing to be that polyimide resin is separated out, so, liberation method be called for simplicity.
When one of this liberation method example is specified, at first, adopt above-mentioned hot method or chemical method to carry out imidization, obtain polyimide resin solution.Then, this polyimide resin solution put into be difficult to dissolve in the poor solvent of this polyimide resin, polyamic acid resin is separated out.Then, the polyimide resin of separating out is carried out drying, obtain the solid polyimide resin.
Adopt this liberation method, no matter the method for imidization adopts hot method or chemical method, consider that from the method for selecting suitable imidization separate out in order to make polyimide resin, it is preferred removing unreacted raw material (monomer) and polyimide resin is made with extra care.Condition when carrying out this liberation method is not particularly limited.Here, as above-mentioned poor solvent, as long as select with the solvent of polyimide resin solution good, and be difficult to dissolve getting final product of polyimide resin, for example, can enumerate acetone, methyl alcohol, ethanol, Virahol, benzene, methylcyclohexane, butanone etc., still, be not limited to these certainly.
Secondly, carry out the method (, being called the decompression method) of imidization as heating under reduced pressure, carry out heat treated and carry out imidization reaction Yi Bian can enumerate by on one side above-mentioned polyamic acid solution being reduced pressure for ease of explanation, simultaneously, make the method for solvent evaporation.Adopt this decompression method, its advantage is because the water that imidization generates can actively be removed outside system, so, the hydrolysis of polyamic acid can be suppressed, thereby the high-molecular weight polyimide resin can be obtained.In addition, adopt this decompression method, can make in the raw material acid dianhydride side or two that exists as impurity survey ring-opening products and close ring once more, so, can expect further to improve the effect of the component of polyimide resin.
Condition when carrying out above-mentioned decompression method is not particularly limited, but the pressure condition when heating condition, decompression, in the present embodiment, for example, it is preferred adopting following condition.
At first, heating condition, preferably in 80～400 ℃ scope, but the lower limit of Heating temperature effectively carries out from imidization, and the consideration that effectively dewaters simultaneously more than 100 ℃ and 100 ℃, is especially preferred more than 120 ℃ and 120 ℃ more preferably.In addition, the top temperature during heating (upper limit of Heating temperature) is preferably below the heat decomposition temperature of purpose polyimide resin.Therefore, as above-mentioned top temperature, finish the temperature of imidization usually, promptly the temperature of degree is preferred in about 250～350 ℃ of scopes.
Secondly, pressure condition during decompression, preferably under alap pressure, more particularly as long as at 0.9～0.001 normal atmosphere (in the scope of 910hPa～1hPa), (be preferred in the scope of 810hPa～1hPa), (in the scope of 710hPa～1hPa) is preferred at 0.7～0.01 normal atmosphere at 0.8～0.001 normal atmosphere.
The rerum natura of＜resulting (A) polyimide resin 〉
Adopt the rerum natura of (A) polyimide resin (particularly soluble polyimide) that above-mentioned manufacture method obtains, be not particularly limited, as long as have the rerum natura that fully is suitable for purposes of the present invention.
For example, as main application of the present invention, can enumerate the matrix material of circuit used in various electronics, electrical equipment machine with fusion, but in the present invention, (A) polyimide resin as main component, with (B) multi-functional cyanate and (C) at least a kind in the epoxy resin mixed, when obtaining the matrix material (compositions of thermosetting resin among the present invention) of above-mentioned fusion, as long as can bring into play for the desired all rerum naturas of the matrix material of this fusion.Certainly, other purposes too.
As main application of the present invention, used circuit desired all rerum naturas aspect the matrix material of fusion in various electronics, electrical equipment machine can be enumerated dielectric characteristics, processibility, thermotolerance, cohesiveness, anti-PCT etc.Here, as (A) polyimide resin of principal constituent, be to give the composition of dielectric characteristics and thermotolerance etc. to the matrix material of fusion, in addition, (A) second-order transition temperature of polyimide resin also exerts an influence to the matrix material processibility of fusion.
The polyimide resin that adopts above-mentioned manufacture method to obtain, its second-order transition temperature is lower, for the processibility that makes the compositions of thermosetting resin that the present invention relates to good, (A) second-order transition temperature of polyimide resin, preferred below 350 ℃ and 350 ℃, more preferably below 320 ℃ and 320 ℃, preferred especially below 280 ℃ and 280 ℃.
In addition, in the present invention, when (A) polyimide resin is cooperated (B) multi-functional cyanate, when each use level (blended amount) is adopted the way that is adjusted in the specialized range, (A) second-order transition temperature of polyimide resin, preferred below 250 ℃ and 250 ℃, more preferably below 200 ℃ and 200 ℃, preferred especially below 180 ℃ and 180 ℃.
As long as (A) second-order transition temperature of polyimide resin is below the above-mentioned upper limit, then in the compositions of thermosetting resin that obtains (matrix material of fusion), just can realize all rerum naturas such as little coefficient of thermal expansion, high heat decomposition temperature, excellent dielectric characteristic, simultaneously because second-order transition temperature is low, so, can under lower temperature, low pressure condition, be pasted processing to clung body each other.The result is to improve the processibility of the compositions of thermosetting resin (matrix material of fusion) that obtains.
＜(B) multi-functional cyanate 〉
Used (B) multi-functional cyanate among the present invention is not particularly limited, and still, particularly considers the preferred at least a kind of multi-functional cyanate that is selected from in the compound of following general formula (6) expression that adopts from this point of excellent heat resistance:
(in the formula, R
7Expression from have singly-bound, aromatic nucleus, at least a kind of divalent organic group of aliphatics ring ,-CH
2-,-C (CH
3)
2-,-C (CF
3)
2-,-CH (CH
3)-,-CH (CF
3)-,-SO
2-,-S-,-select among the O-, R
8, R
9Identical or different respectively, and be selected from-H ,-CH
3,-CF
3, o represents 0～7 integer, p, q are identical or different, and represent 0～3 integer).
In multi-functional cyanate, from considering, from following group (7) with the intermiscibility height (easily mixing) and the facile reason of polyimide resin with above-mentioned general formula (6) expression:
It is preferred selecting at least a kind of use in the compound of (in the formula, r and t represent 0～5 integer) expression, particularly adopt with following structural represent 2, two (the 4-cyanate radical phenyl) propane of 2-are more preferably:
As above-mentioned (B) multi-functional cyanate, can adopt the compound of representing with above-mentioned general formula (6) as monomer.In addition, also can wait and to be transformed into the oligopolymer of three azine rings (cyanate ester based tripolymer) with the cyanate ester based part in the compound (monomer) of above-mentioned general formula (6) expression, also can be used as above-mentioned (B) multi-functional cyanate by heating.In addition, as above-mentioned (B) multi-functional cyanate, also can and use with above-mentioned monomer and oligopolymer.
Multi-functional cyanate as above-mentioned oligopolymer, have no particular limits, concrete, for example, can enumerate and make 2, whole cyanate ester based 5～50% of two (4-cyanate radical phenyl) propane of 2-react be transformed into three azine rings oligopolymer (for example, the trade(brand)name BA200 that ロ Application ザ society makes, the trade(brand)name Arocy B-30 that rising sun チ バ society makes, B-50 etc.), two (3,5-dimethyl-4-cyanate phenyl) whole cyanate ester based 5～50% of methane reacts, be transformed into oligopolymer (for example, the trade(brand)name Arocy M-30 of rising sun チ バ society manufacturing of three azine rings, M-50 etc.).
＜(A) and (B) blending ratio 〉
In compositions of thermosetting resin of the present invention, as the thermoset composition, as long as contain above-mentioned (B) multi-functional cyanate (monomer and/or its oligopolymer), even during other any compositions beyond containing this composition, (A) polyimide resin and (B) ratio of mixture of multi-functional cyanate (blending ratio), as long as just there is no particular limitation in the scope of not damaging dielectric characteristics, but according to desired rerum natura, can enumerate following preferred range.
Concrete, above-mentioned (A) polyimide resin is reached (B) any composition of multi-functional cyanate, each ratio of mixture can get final product by the purposes and working method adjusted of compositions of thermosetting resin, but when the ratio of mixture of (A) polyimide resin is high, can improve dielectric characteristics, on the other hand, when the ratio of mixture of (B) multi-functional cyanate is high, can improve cohesiveness and processibility.
Yet, the good occasion of balance in cohesiveness (with the cohesiveness of conductors such as Copper Foil) and thermotolerance (Young's modulus of compositions of thermosetting resin and linear expansivity etc. during high temperature) etc., (B) in weight ratio (mass ratio), what be in following scope is preferred to multi-functional cyanate to the ratio of (A) polyimide resin.
C
A: C
B=20: 80～90: 10 (preferred range)
=30: 70～80: 20 (preferred scopes)
=50: 50～75: 25 (especially preferred scopes)
When departing from the scope of above-mentioned ratio of mixture, for resulting compositions of thermosetting resin, diminish the danger of the important rerum natura of the matrix material of using as various wiring substrates such as dielectric characteristics, cohesiveness, thermotolerance, the processibility when on conductor or circuit substrate, pasting etc. with conductor.That is, in the compositions of thermosetting resin of the present invention, when (A) polyimide resin mixes when too much, the flowability of compositions of thermosetting resin descends during heating, the processibility variation when fitting by heating.Otherwise,, make cohesiveness and dielectric characteristics impaired when (B) multi-functional cyanate mixes when too much.
, the inventor finds first, and (A) the polyimide resin blending ratio is higher, and anti-PCT (PCT handle before and after PCT handles, with the cohesiveness of conductor such as Copper Foil) is higher.
Therefore, particularly resulting compositions of thermosetting resin, when in the purposes of raising, using as important parameter with the PCT characteristic, in weight ratio (mass ratio), (B) multi-functional cyanate is in to the ratio of mixture (ratio of components) of (A) polyimide resin that the person is preferred in the following scope.Also have, in following formula, C
AThe weight of the full composition of expression (A) polyimide resin, C
BThe weight of the full composition of expression (B) multi-functional cyanate.
C
A∶C
B＝95∶5～85∶15
If ratio of mixture is in above-mentioned scope, anti-PCT and processibility (applying adds the processibility in man-hour) can reach good balance.In addition, if ratio of mixture in above-mentioned scope, during actual the use, can also be brought into play the cohesiveness of abundant tolerance degree.
In contrast, when departing from above-mentioned ratio of mixture scope, for resulting compositions of thermosetting resin, diminish as various wiring substrates with the important rerum natura of matrix materials as with the cohesiveness of conductor or circuit substrate, the danger of processibility when fitting with conductor or circuit substrate.That is, in compositions of thermosetting resin of the present invention, when (A) polyimide resin mixed too much (surpassing 95 weight %), the flowability during heating reduced, and the processibility when causing fitting owing to heating worsens.
In addition, above-mentioned (B) multi-functional cyanate is owing to be the thermoset composition, so in the compositions of thermosetting resin that obtains, in order to present good thermoset, (B) amount of multi-functional cyanate is at 5 weight % be preferred more than the 5 weight %.Otherwise, in the compositions of thermosetting resin that the present invention relates to, when (B) multi-functional cyanate mixed too much (surpassing 15 weight %), the cohesiveness after the cohesiveness of resulting compositions of thermosetting resin, particularly PCT are handled reduced (anti-PCT is impaired).
＜(B) curing catalysts of multi-functional cyanate 〉
In compositions of thermosetting resin of the present invention, when adopting (B) multi-functional cyanate (monomer and/or its oligopolymer) as the thermoset composition, in order to promote the curing of this (B) multi-functional cyanate, can adopt curing catalysts (or curing catalyst, for ease of distinguishing clearly, be called the cyanate curing catalysts) with following epoxy hardener and curable epoxide promotor.
That is, when adopting compositions of thermosetting resin of the present invention, present till the degree of excellent dielectric characteristic after must making (B) multi-functional cyanate be cured to curing.Therefore, for carrying out the curing reaction of (B) multi-functional cyanate, sometimes need be under the high temperature more than 200 ℃ and 200 ℃ and carry out more than 1 hour and 1 hour the preferred curing reaction time more than 2 hours and 2 hours.In order to promote the curing reaction of (B) multi-functional cyanate, preferably adopt the cyanate curing catalysts here.
As above-mentioned cyanate curing catalysts, as long as can promote the compound of the reaction of (B) multi-functional cyanate to be not particularly limited.Concrete, can enumerate metal species catalyzer such as zinc acetylacetonate (II), zinc naphthenate, acetylacetone cobalt (II), acetylacetone cobalt (III), cobalt naphthenate, acetylacetone copper (II), copper naphthenate; N-(4-hydroxy phenyl) maleimide, right-tert-octyl phenol, cumyl phenol, resol etc. have the organic compound of hydroxyl; Deng.These cyanate curing catalysts both can use separately, but also used after the appropriate combination.
Even in above-mentioned cyanate curing catalysts, consider from promoting better to solidify, it is preferred adopting the metal species catalyzer, particularly, it is preferred adopting zinc acetylacetonate (II), zinc naphthenate, acetylacetone cobalt (II), acetylacetone cobalt (III), cobalt naphthenate, acetylacetone copper (II), copper naphthenate, wherein, zinc acetylacetonate (II), acetylacetone copper (II) are especially preferred.
The use level of above-mentioned cyanate curing catalysts (usage quantity combined amount) because of the kind of used cyanate curing catalysts and promote that the degree of curing reaction is different, is not particularly limited.For example, if the cyanate curing catalysts is above-mentioned metal species catalyzer, it is preferred using in the scope of 0.001～2 weight part (or mass parts) with respect to (B) multi-functional cyanate 100 weight parts so.In the scope of 0.001～0.1 weight part, use and be more preferably.In addition, when being above-mentioned organic compound as the cyanate curing catalysts, it is preferred using in the scope of 0.1～20 weight part with respect to (B) multi-functional cyanate 100 weight parts.
Particularly, when adopting zinc acetylacetonate (II) or acetylacetone copper (II) as the cyanate curing catalysts, it is preferred using in the scope of 0.001～0.5 weight part (or mass parts) with respect to (B) multi-functional cyanate 100 weight parts, and it is preferred using in the scope of 0.001～0.05 weight part.When the consumption of cyanate curing catalysts is lower than above-mentioned scope, be difficult to obtain promoting the effect of curing reaction, when being higher than above-mentioned scope, the storage stability of resulting compositions of thermosetting resin might be impaired, is unfavorable.
＜(C) epoxy resin 〉
Whether (C) epoxy resin that uses among the present invention depends on and is used as (B) multi-functional cyanate of thermoset composition and makes the scope difference of used kind.
At first,,, the kind of used (C) epoxy resin is not particularly limited, can adopts Resins, epoxy arbitrarily in (B) multi-functional cyanate and (C) epoxy resin and time spent as the thermoset composition.Concrete can enumerate, for example, bisphenol-type epoxy resin, halogenated bisphenol based epoxy resin, novolak based epoxy resin, alkyl novolak based epoxy resin, polyethylene glycols Resins, epoxy, cyclic aliphatic epoxy resin, cresols novolak based epoxy resin, glycidyl amine epoxy resin, urethane-modified Resins, epoxy, rubber modified epoxy resin, epoxy-modified polysiloxane, following suitable Resins, epoxy (with the preferred Resins, epoxy of following general formula (8), (9) and/or (10) expression) etc.Above-mentioned Resins, epoxy both can have been distinguished separately and use, and also can be used in combination more than 2 kinds and 2 kinds as required.
In above-mentioned Resins, epoxy, good this point of thermotolerance, cohesiveness, intermiscibility, insulativity, the dielectric characteristics rerum naturas such as (low-k, low-dielectric loss tangents) of (easiness in one's hands) and resulting compositions of thermosetting resin of particularly being easy to get calmly considers that it is preferred adopting suitable Resins, epoxy.
Secondly, as the thermoset composition, when also not using (B) multi-functional cyanate, promptly, at least employing (A) polyimide resin and (C) epoxy resin, but when not adopting (B) multi-functional cyanate, can adopt to be selected from Resins, epoxy of representing with following general formula (8), (9) and (10) and/or at least a kind of Resins, epoxy of silane-modified Resins, epoxy that contains alkoxyl group:
(above-mentioned various in, G represents the organic group represented with following structural:
I, j, k be the integer of independent expression 0～5 respectively, R
10, R
11, R
12, R
13The alkyl that independent respectively expression hydrogen atom or carbonatoms are 1～4).Resins, epoxy with these general formulas (8), (9) and (10) expression, with (B) multi-functional cyanate and time spent also be suitable Resins, epoxy, so, as mentioned above, in the present invention, these Resins, epoxy of representing with general formula are called " suitable Resins, epoxy ".
Here, the so-called above-mentioned silane-modified Resins, epoxy that contains alkoxyl group is meant part or all of the hydroxyl that contains, with the Resins, epoxy of alkoxysilane compound containing trialkylsilyl group in molecular structure reaction in Resins, epoxy.For example, specifically can enumerate the Resins, epoxy that has with following general formula (11) expression structure:
(w represents the integer more than 1 in the formula).
As above-mentioned suitable Resins, epoxy, from dielectric characteristics (low-k, low-dielectric loss angle tangent), thermotolerance, viewpoint such as obtain easily, the Resins, epoxy of the mean value of k in 0～2 scope is preferred in the use formula.As this Resins, epoxy, concrete, can enumerate trade(brand)name EXA7200 (k average out to 0.3) that for example big Japanese イ Application キ chemical industry society makes and trade(brand)name EXA7200H (k average out to 1) etc.In addition, concrete as based on containing of bisphenol A type epoxy resin of alkoxysilane-modified Resins, epoxy, can enumerate the trade(brand)name コ Application Port セ ラ Application E series that for example waste Chuan Huaxuegongyeshe makes etc.
Also have,, consider that from the viewpoint of reliability of electrical insulating property it is preferred adopting the high Resins, epoxy of purity as (C) epoxy resin that uses among the present invention.Concrete is, halogen element in the Resins, epoxy and alkali-metal content concn, and it is preferred extracting at 25ppm with below the 25ppm under 120 ℃, 2 normal atmosphere, is preferred at 15ppm with below the 15ppm.As described in the upper limit and below the upper limit, can judge the Resins, epoxy purity height among the present invention.In addition, be suitable.On the other hand, when halogen element and alkali-metal content concn surpassed 25ppm, the reliability of the compositions of thermosetting resin that the present invention relates to had impaired danger, is unfavorable.
As mentioned above, in the present invention, as the Resins, epoxy of (C) epoxy resin, with (B) multi-functional cyanate and time spent, be not limited to above-mentioned suitable Resins, epoxy.Particularly, in the present invention, for cohesive force and the thermotolerance that improves resulting compositions of thermosetting resin, can also adopt above-mentioned suitable Resins, epoxy Resins, epoxy in addition (in the following description, for simplicity, be called " Resins, epoxy of the heat-resisting raising usefulness that bonds ").
Resins, epoxy as the heat-resisting raising usefulness of above-mentioned bonding, be not particularly limited, concrete, for example, can enumerate bisphenol-type epoxy resin, the halogenated bisphenol based epoxy resin, the novolak based epoxy resin, allyl group novolak based epoxy resin, alkyl novolak based epoxy resin, the biphenyl based epoxy resin, the naphthalene based epoxy resin, polyethylene glycols Resins, epoxy, cyclic aliphatic epoxy resin, cresols novolak based epoxy resin, the glycidyl amine epoxy resin, urethane-modified Resins, epoxy, rubber modified epoxy resin, epoxy-modified polysiloxane etc.
The Resins, epoxy of these heat-resisting raising usefulness that bond both can use separately, also can appropriate combination use more than 2 kinds and 2 kinds.In addition, the use level of the Resins, epoxy of these heat-resisting raising usefulness that bond (usage quantity combined amount) is not particularly limited, as long as in the not impaired scope of the dielectric characteristics of resulting compositions of thermosetting resin, but preferably, become component (not only to comprise (C) epoxy resin with respect to all resins, comprise that also above-mentioned (A) polyimide resin and following (D) are equivalent to the resene of other compositions) 100 weight parts, use in the scope of about 1～5 weight part.When the use level of the Resins, epoxy of the heat-resisting raising usefulness of above-mentioned bonding is lower than 1 weight part, be difficult to obtain close-burning raising effect, otherwise when use was higher than 5 weight parts, dielectric characteristics was impaired.
Also have, the Resins, epoxy of the heat-resisting raising usefulness of above-mentioned bonding, same with above-mentioned suitable Resins, epoxy, high purity is preferred, concrete is that it is preferred that halogen element in the resin and basic metal equal size concentration are in the interior person of above-mentioned scope.
In addition, (C) epoxy resin that uses among the present invention, self-evident, be not limited to the above-mentioned suitable Resins, epoxy and the Resins, epoxy of the heat-resisting raising usefulness that bonds.Therefore, according to purposes, the above-mentioned suitable Resins, epoxy and the Resins, epoxy of the heat-resisting raising usefulness that bonds, both can with Resins, epoxy and the usefulness beyond these, also can be replacing the Resins, epoxy beyond these of suitable Resins, epoxy to use as main (C) epoxy resin.
＜(A) and (C) or (A), (B) and blending ratio (C)
In compositions of thermosetting resin of the present invention, if contain above-mentioned (C) epoxy resin as the thermoset composition, even when containing any other compositions beyond this composition, (A) polyimide resin and (C) ratio of mixture of epoxy resin (blending ratio), as long as in the scope of not damaging dielectric characteristics, just be not particularly limited, but, can enumerate following preferred range according to desired rerum natura.
At first, at least adopt (A) polyimide resin and (C) epoxy resin is (at this moment, suitable Resins, epoxy), but when not adopting (B) multi-functional cyanate, in weight ratio (mass ratio), (C) epoxy resin is in to the ratio of mixture (ratio of components) of (A) polyimide resin that the person is preferred in the following scope.Also have, in following formula, C
CThe weight of the full composition of expression (C) epoxy resin.
C
A: C
C=50: 50～99: 1 (preferred range)
=60: 40～95: 5 (preferred scopes)
=75: 25～90: 10 (especially preferred scopes)
If in the scope of above-mentioned ratio of mixture, the balance of cohesiveness (with the cohesiveness of conductors such as Copper Foil) and thermotolerance (Young's modulus of compositions of thermosetting resin and linear expansivity etc. during high temperature) etc. is good.
In contrast, when departing from the scope of above-mentioned ratio of mixture, when adopting resulting compositions of thermosetting resin, diminish the important rerum natura of the matrix material of using as various wiring substrates, as dielectric characteristics, with the cohesiveness of conductor, thermotolerance, the danger of processibility etc. when conductor or circuit substrate are closed in stickup.That is, in compositions of thermosetting resin of the present invention, when (A) polyimide resin mixes when too much, the flowability of the compositions of thermosetting resin during heating descends, and fashionable processibility variation is pasted in heating.Otherwise when (C) epoxy resin mixes when too much, dielectric characteristics is impaired.
Secondly, as the thermoset composition, in (B) multi-functional cyanate and (C) epoxy resin and time spent, promptly, adopting (A) polyimide resin, (B) multi-functional cyanate (monomer and/or its oligopolymer) and (C) epoxy resin and time spent, in weight ratio (mass ratio), (A) polyimide resin, (B) multi-functional cyanate and (C) each ratio of mixture (ratio of components) of epoxy resin be preferred in following scope.
C
A/(C
A+C
B+C
C)＝0.5～0.96
C
B/(C
A+C
B+C
C)＝0.02～0.48
C
C/(C
A+C
B+C
C)＝0.002～0.48
If in the scope of above-mentioned ratio of mixture, the balance of cohesiveness (with the cohesiveness of conductors such as Copper Foil) and thermotolerance (Young's modulus of compositions of thermosetting resin and linear expansivity etc. during high temperature) etc. is good.
In contrast, when departing from the scope of above-mentioned ratio of mixture, when adopting resulting compositions of thermosetting resin, diminish the important rerum natura of the matrix material of using as various wiring substrates, as dielectric characteristics, with the cohesiveness of conductor, thermotolerance, the danger of processibility etc. when pasting conductor or circuit substrate.That is, in compositions of thermosetting resin of the present invention, when (A) polyimide resin mixes when too much, the flowability of the compositions of thermosetting resin during heating descends, the processibility variation when heating is pasted.Otherwise when (C) epoxy resin mixes when too much, cohesiveness and dielectric characteristics are impaired.In addition, when (C) epoxy resin mixes when too much, dielectric characteristics is impaired.
In addition, in order in resulting compositions of thermosetting resin, to present thermoset, as the amount of the epoxy resin of (B) multi-functional cyanate of thermoset composition+(C) at least at 4 weight % be preferred more than the 4 weight %.
＜(C) solidifying agent of epoxy resin 〉
In compositions of thermosetting resin of the present invention, adopt (C) Resins, epoxy time-like as the thermoset composition, identical with the situation of above-mentioned (B) multi-functional cyanate, in order to promote the curing of (C) epoxy resin, can adopt the solidifying agent (, being called epoxy hardener) of used for epoxy resin for ease of more clearly distinguishing over above-mentioned cyanate curing catalysts.
As above-mentioned epoxy hardener, be not particularly limited, but it is concrete, for example, can enumerate two (4-aminophenyl) sulfones, two (4-aminophenyl) methane, 1,5-diaminonaphthalene, Ursol D, mphenylenediamine, O-Phenylene Diamine, 2,6-two chloro-1,4-phenylenediamine, 1, aromatic diamine compounds such as 3-two (right-aminophenyl) propane, m-xylenedimaine; Quadrol, diethylenediamine, four ethylidene pentammines, diethyl amino propylamine, hexamethylene-diamine, the Meng fatty amine compounds such as diamines, isophorone diamine, two (4-amino-3-methyl bicyclic hexyl) methane, polymethylene diamines, polyether diamine; Aliphatic anhydride such as polyaminoamide compounds, dodecyl succinic anhydride, poly-adipic anhydride, poly-nonane diacid acid anhydride; Ester ring type such as hexahydro phthalic anhydride, methyl hexahydro phthalic anhydride acid anhydrides; Aromatic anhydrides such as Tetra hydro Phthalic anhydride, trimellitic acid 1,2-anhydride, benzophenone tetracarboxylic acid, ethylene glycol bis trimellitate, glycerol three trimellitates; The halogenide of novolac resins such as phenol, cresols, alkylphenol, Trivalin SF, dihydroxyphenyl propane, Bisphenol F and these resol; Resol class, aminoresin class, urea resin class, melamine resin class, dicyano diamide, two hydrazine compound classes, imidazolium compounds class, Lewis acid and cloth youth Si Taide Barbiturates, poly-thiol compound class, isocyanic ester and blocked isocyanate compounds class; Deng.
These epoxy hardeners both can have been distinguished separately and use, and also can be used in combination more than 2 kinds and 2 kinds as required.In addition, the use level of above-mentioned epoxy hardener (usage quantity combined amount) also is not particularly limited, generally being with respect to (C) epoxy resin 100 weight parts, is preferred in the scope of 5～200 weight parts, is preferred with the epoxy equivalent (weight) equivalent person of cooperation particularly.
In addition, in compositions of thermosetting resin of the present invention, in order to promote the reaction of (C) epoxy resin and above-mentioned epoxy hardener, can be as required, can be simultaneously also with above-mentioned epoxy hardener and curing catalyst (, being called curable epoxide promotor) for ease of more clearly distinguishing over the cyanate curing catalysts.
As above-mentioned curable epoxide promotor, there is no particular limitation, but it is concrete, for example, can enumerate triphenylphosphine, tertiary amines, trimethanolamine, trolamine, the tetrem hydramine, 1,8-diaza-dicyclo [5,4,0]-7-11 carbon tetraphenyl borate salts, imidazoles, the 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, the 2-phenylimidazole, the 2-undecyl imidazole, 1 benzyl 2 methyl imidazole, 2-heptadecyl imidazoles, 2 isopropyl imidazole, 2, the 4-methylimidazole, 2-phenyl-4-methylimidazole, the methylimidazole quinoline, 2-ethyl imidazol(e) quinoline, the 2 isopropyl imidazole quinoline, the 2-benzylimidazoline, 2-undecyl imidazole quinoline, 2,4-methylimidazole quinoline, 2-phenyl-4-methylimidazole quinoline etc.
These curable epoxide promotor both can have been distinguished separately and use, and also can be used in combination more than 2 kinds as required.In addition, the use level (usage quantity combined amount) of above-mentioned curable epoxide promotor also being not particularly limited, still, is preferred with respect to (C) epoxy resin 100 weight parts in 0.01～10 weight part scope generally.
＜(D) other compositions 1: other resins 〉
In compositions of thermosetting resin of the present invention, contain above-mentioned (A) polyimide resin as main component, and contain as above-mentioned (B) the multi-functional cyanate of thermoset composition and (C) at least a kind of epoxy resin, other compositions are not particularly limited.Therefore, in compositions of thermosetting resin of the present invention, can also contain above-mentioned (A) (B) (C) composition (, being called (D) other compositions) in addition for ease of explanation.
Concrete, for example,, can enumerate (D-1) other type thermosetting resins as one of above-mentioned (D) other compositions example.Should (D-1) other type thermosetting resins, with above-mentioned (B) multi-functional cyanate (monomer and/or its oligopolymer) and (C) epoxy resin is same, also can be used as the thermoset composition.If and/or (C) and usefulness, then can improve all characteristics such as the cohesiveness of resulting compositions of thermosetting resin and thermotolerance, processibility with this (D-1) other type thermosetting resins and above-mentioned (B).
As thermosetting resin as above-mentioned (D-1) other type thermosetting resins, concrete, for example, can enumerate thermosetting resins such as bimaleimide resin, diallyl imide (PVC ス ア リ Le Na ジ イ ミ De) resin, resol, acrylic resin, methacrylic resin, hydrogenation silyl cured resin, allyl group cured resin, unsaturated polyester resin; The thermosetting polymer of the side chain of macromolecular chain or terminal side chain reactive group type with allyl group, vinyl, alkoxysilyl, hydrogen silyl isoreactivity group etc.; Deng.
These (D-1) other type thermosetting resins both can use separately, also can be more than 2 kinds or 2 kinds in addition appropriate combination use.In addition, the use level of these (D-1) other type thermosetting resins (usage quantity combined amount) also is not particularly limited, as long as in the scope of the dielectric characteristics of not damaging resulting compositions of thermosetting resin.
＜(D) other compositions 2: organic solvent 〉
Concrete, for example,, can enumerate (D-2) organic solvent class as one of described (D) other compositions example.Should (D-2) organic solvent class by adopting, in the thermosetting resin that obtains, in that being pasted each other, clung body adds man-hour, can improve the flowability of compositions of thermosetting resin.
As above-mentioned (D-2) organic solvent class, so long as can dissolve compositions of thermosetting resin of the present invention, promptly, (A) various compositions such as polyimide resin, (B) multi-functional cyanate, (C) epoxy resin, (D-1) other type thermosetting resins organic solvent can there is no particular limitation, but the wherein preferred organic solvent of boiling point below 200 ℃ and 200 ℃.
Concrete, for example preferably adopt ring-type ethers such as tetrahydrofuran (THF), dioxolane, diox; Ethers such as chain ether such as glycol dimethyl ether, ト リ グ ラ イ system, glycol ether, ethyl cellosolve, methylcyclohexane.In addition, blended mixed solvent such as above-mentioned ethers and toluene, xylene, glycols, N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, annular siloxane, chain siloxanes etc. in addition also can preferably use.
As described below, for compositions of thermosetting resin of the present invention, can be in the state (B scalariform attitude) before solidifying sometimes according to purposes.At this moment, as long as compositions of thermosetting resin pressurization and heating to being in B scalariform attitude, then this compositions of thermosetting resin flows in the gap (for example, the gap of circuit etc.) etc. of clung body.At this moment, compositions of thermosetting resin with what degree flows, and to be filled in the gap etc. be important factor.The inventor finds that alone organic solvent contained in this compositions of thermosetting resin brings very big influence to flowability.
That is, in compositions of thermosetting resin of the present invention, the flowability when controlling pressurized, heated, it is preferred containing organic solvent in the compositions of thermosetting resin.In other words, to compositions of thermosetting resin of the present invention, the positive effect that contains organic solvent is, controls its flowability.
In compositions of thermosetting resin of the present invention, the organic solvent amount that cooperates for the flowability of realizing ideal can suitably be set and is not particularly limited, still, general 1～20 weight % preferably, 3～10 weight % are more preferably.As in this scope, can bring into play sufficient flowability.
＜compositions of thermosetting resin 〉
Compositions of thermosetting resin of the present invention, be above-mentioned (A) polyimide resin, (B) multi-functional cyanate and/or (C) epoxy resin mixed, can sneak into above-mentioned (D) other compositions as required, its manufacture method is not particularly limited.
In addition, compositions of thermosetting resin of the present invention, at least contain above-mentioned (A) polyimide resin, (B) multi-functional cyanate and/or (C) epoxy resin, also can contain (D) other compositions, its state and shape are not particularly limited according to purposes etc.That is, the concrete operational version of compositions of thermosetting resin of the present invention, the interior the whole bag of tricks of scope that can adopt the practitioner to implement, and be not particularly limited.
At first, the concrete state of compositions of thermosetting resin of the present invention being not particularly limited, can be solid, the also solution that solid product can be made, or solid phase prod made other state.
When compositions of thermosetting resin of the present invention is solution, promptly, compositions of thermosetting resin of the present invention is dissolved in the solvent, when using as resin solution, as used solvent, get final product and be not particularly limited so long as can dissolve the solvent of compositions of thermosetting resin of the present invention, but the preferred solvent of boiling point below 150 ℃ and 150 ℃.Concrete, preferably can adopt ethers and/or its mixed solvent enumerated in above-mentioned (D-2) organic solvent class.
Compound method when solid-state compositions of thermosetting resin is made solution (manufacture method) is not particularly limited, but, concrete, for example, can enumerate various compositions that constitute compositions of thermosetting resin of the present invention (above-mentioned (A) (B) (C) etc.) are added in the above-mentioned solvent respectively, are stirred the method for making; In advance above-mentioned various compositions with separately dissolution with solvents, make dissolved composition solution after, these composition solution blended manufacture method etc. in addition.
In addition, even when compositions of thermosetting resin of the present invention is solid-state, also can contain above-mentioned solvent.For example, as described below, when compositions of thermosetting resin is resin sheet or resin molding, in order to control the flowability of this compositions of thermosetting resin, as above-mentioned＜(D) other compositions 2: organic solvent〉explanation in the joint, also can contain all kinds of SOLVENTS in advance.
Therefore, compositions of thermosetting resin of the present invention also can contain (D-2) organic solvent, and as a kind of composition in this compositions of thermosetting resin, perhaps, in other words the composition that does not contain in this compositions of thermosetting resin also can as outer added ingredients.
Secondly, when being solid-state, its concrete shape is not particularly limited, for example, is shaped in advance to use behind sheet or membranaceous resin sheet and the resin molding and also can at compositions of thermosetting resin of the present invention.
Here so-called above-mentioned resin sheet and resin molding are that the compositions of thermosetting resin of invention is processed into sheet or membranaceous, as its concrete form, can enumerate single-layer sheet, 2 layers or 3 synusia, multilayer tablet etc.Single-layer sheet is the sheet that only is made of compositions of thermosetting resin, and 2 layers or 3 synusia are on the single face or two sides of the film (base material film) that constitutes base material, the resin layer that formation is made of compositions of thermosetting resin of the present invention and the sheet made, multilayer tablet are the resin layer alternatively laminated that base material film and compositions of thermosetting resin are constituted and the sheet that obtains.
As the advantage of above-mentioned resin sheet, can enumerate following example.For example, as one of purposes of compositions of thermosetting resin of the present invention, can enumerate and be used for making the laminated product of the such multiple stratification of harness substrate or the purposes of circuit substrate.At this moment, compositions of thermosetting resin of the present invention is the state (B scalariform attitude) that is in before solidifying, and by with its pressurization and/or heating, makes compositions of thermosetting resin flow into the gap of circuit (being made of conductors such as copper).At this moment, compositions of thermosetting resin is if resin sheet or resin molding, and then these resin sheets or resin molding also can be stacked on the circuit.
If compositions of thermosetting resin is a resin solution, then on circuit (forming the substrate of this circuit) surface, coating resin solution, formation stratiform are made, but, if compositions of thermosetting resin of the present invention is resin sheet or resin molding, then behind the adherend superimposed layer, only get final product by pressurization and/or heating, and must painting process.Therefore, can obtain simplifying the effect of the manufacturing process etc. of laminated product.Certainly, must think, preferably, adopt resin solution according to the shape of laminated product.
Manufacture method to above-mentioned resin sheet and/or resin molding is not particularly limited, but when generally adopting single-layer sheet, the resin solution that adopts above-mentioned manufacture method to obtain curtain coating or be coated with (resin solution painting process) on supporting body surface, then, the resin solution of coating is carried out drying (drying process), and the sheet that drying is obtained is peeled off (stripping process) and is made from supporter.
In addition, when 2 layers or 3 synusia,, then, the resin solution of coating is carried out drying (drying process) form resin layer and make above-mentioned resin solution (single face or two sides) curtain coating or be coated with (resin solution painting process) on the base material film surface.In addition, when being multilayer tablet, be in above-mentioned 2 layers or 3 synusia manufacturing processes, the sheet that is in the state before drying process lamination and making in addition.
In addition, when compositions of thermosetting resin of the present invention used as resin sheet or resin molding, this resin sheet or resin molding also can be the fiber strengthening types.The fiber that uses in the resin sheet as the fiber strengthening type, concrete, for example, can enumerate woven fiber glass, glassmat, aromatic polyamide fibre cloth, aromatic polyamide fibre felt etc., but be not particularly limited.As the manufacture method of fiber strengthening type resin sheet, can enumerate a fiber impregnation in wax (resin solution), make the method for resin solution semicure, peculiarly Xian Ding not but.
＜post-heating is handled 〉
In compositions of thermosetting resin of the present invention, as the thermoset composition, when containing (B) multi-functional cyanate, when this multi-functional cyanate is haplotype, perhaps, under the situation that contains (C) epoxy resin, the processing of bonding back enforcement post-heating is preferred on clung body.Handle by implementing this post-heating, the curing reaction of multi-functional cyanate of haplotype and epoxy resin is fully carried out.
The actual conditions that post-heating is handled is not particularly limited, for example, when the thermoset composition is the multi-functional cyanate of haplotype, Heating temperature in 150～250 ℃ scope, about 10 minutes～3 hours scope heat-up time condition in 1～3 hour scope more preferably from about, be one of appropriate condition example.On the other hand, be the Resins, epoxy time-like at the thermoset composition, Heating temperature in 150～200 ℃ scope, heat-up time about 10 minutes～3 hours scope condition, be one of appropriate condition example.
The dielectric characteristics of＜thermosetting resin 〉
When adopting compositions of thermosetting resin of the present invention, when specific inductivity that records when cured and dielectric loss tangent are in the following scope, can judge that it has good low dielectric characteristics.Promptly, when adopting compositions of thermosetting resin of the present invention, under the temperature condition in 200～250 ℃ of scopes, heated when being cured in 1～5 hour, the specific inductivity when frequency 1～10GHz is below 3.5 and 3.5, below preferred 3.2 and 3.2, more preferably below 3.0 and 3.0, the dielectric loss tangent of this moment is below 0.010 and 0.010, below preferred 0.015 and 0.015, more preferably below 0.012 and 0.012.
If dielectric characteristics in above-mentioned scope, when manufacturing has the circuit substrate of trickle distribution, adopts compositions of thermosetting resin of the present invention, also can keep the electric reliability of trickle distribution, and can make the signal velocity high speed of circuit.
Also have, in compositions of thermosetting resin of the present invention, can also contain above-mentioned composition in addition under the situation that does not reduce its characteristic, this is self-evident.Equally, in compositions of thermosetting resin of the present invention, can also contain above-mentioned operation in addition, this also is self-evident.
＜laminated product circuit substrate 〉
As laminated product of the present invention, just be not particularly limited as long as contain compositions of thermosetting resin of the present invention.Concrete, for example, can enumerate above-mentioned 2 layers or resin sheets such as 3 synusia and multilayer tablet, metal foil laminates goods etc.
Above-mentioned metal foil laminates goods are on the single face or two sides of metal levels such as copper or aluminium, form the resin layer (for ease of explanation, only being called for short resin layer) contain compositions of thermosetting resin of the present invention and constitute.Can enumerate more specifically, preferably have resin layer more than 1 layer and the laminated product of metal foil layer more than 1 layer, for example, on the single face of tinsel, resin layer is set and the 2 layer laminate goods that constitute; Have at least 1 layer of tinsel and resin layer and more than 1 layer, tinsel and resin layer be the laminated product of lamination in addition alternately; Deng.
Manufacture method to above-mentioned metal foil laminates goods is not particularly limited, for example, in the manufacture method of above-mentioned metal foil laminates goods, can adopt and 2 layers or 3 synusia, or the same method of the manufacture method of multilayer tablet.Concrete is that above-mentioned resin solution (single face or two sides) on metal foil surface is carried out curtain coating or coating (resin solution painting process), then, the resin solution of curtain coating or coating is carried out drying (drying process) formation resin layer and makes.
As other manufacture method, can enumerate above-mentioned resin sheet is sticked on method on the metal foil surface.At this moment, as resin sheet, both can be to paste single-layer sheet, also can be to paste 2 layers or 3 synusia or multilayer tablet.As other manufacture method, can enumerate the method that on above-mentioned resin sheet, forms tinsel by electroless plating or sputtering method etc.
As above-mentioned tinsel, get final product so long as can be used as the metal of circuit substrate conductor, its concrete formation is not particularly limited, generally speaking, as mentioned above, can enumerate the paper tinsel that materials such as copper and aluminium constitute.In addition, the thickness of tinsel also is not particularly limited, can sets suitable thickness according to formed circuit kind.
Circuit substrate of the present invention can be by to the tinsel (conductor layer) in the above-mentioned metal foil laminates goods, and the circuit etc. that adopts method such as metal etch to form desirable pattern is made.The concrete grammar of used metal etch is not particularly limited to this moment, still, preferably can suitably adopt methods such as dry film protective layer or liquid protective layer.In addition, the pattern to circuit also is not particularly limited.
Below, illustrate in greater detail the present invention according to specific embodiment, but these embodiment just are used to illustrate one of the present invention example, do not limit the present invention.Particularly, for the following example, for more clearly being described, effect of the present invention enumerates a plurality of comparative examples, but these comparative examples not only are the example beyond the scope of the invention entirely, and, for the concrete selection scheme of more detailed description the present invention, also generally contain introducing as additional as the partial content of " comparative example " with which easily.Thereby claim scope of the present invention is not limited by the following example and comparative example, and the practitioner can do all changes, correction and change not departing under the scope of the invention situation.
Also have, the dielectric characteristics and the thermal property of the resin combination after solidifying in the second-order transition temperature of the polyimide resin that obtains with following synthesis example, embodiment and the compositions of thermosetting resin that obtains with comparative example, and the Copper Foil stripping strength with metal foil laminates plate of the resin layer that contains above-mentioned compositions of thermosetting resin is carried out evaluation of measuring by following method.
[second-order transition temperature]
As determinator, can adopt dynamic viscoelastic evaluating apparatus DMS200 (trade(brand)name, セ イ コ one イ Application ス Star Le メ Application Star (strain) system), adopt following condition determination to measure.Also have, resulting tan δ peak temperature as second-order transition temperature.
Measure temperature range: 30～350 ℃
Sample shape: 9mm * 40mm
Measure frequency: 5Hz
[dielectric characteristics]
As determinator, adopt empty syntonizer perturbation method multiparameter specific inductivity evaluating apparatus (trade(brand)name, (strain) Northeast electronic application exploitation society makes), adopt following condition determination to measure specific inductivity and dielectric loss tangent.
Measure frequency: 3GHz, 5GHz, 10GHz
Measure temperature: 22～24 ℃
Measure humidity: 45～55%
Measure sample: use the sample of under the said determination condition, placing 24 hours.
[thermal property]
Measure thermal expansivity in order to estimate thermal property.Thermal expansivity adopts TMA-50 (trade(brand)name, Shimadzu Seisakusho Ltd. makes), measures under following condition determination, the coefficient of thermal expansion of the evenly heat rate of expansion in 100～200 ℃ of scopes in the measurement result as sample.
Measuring method: stretching mode (be adjusted to and increase the weight of 0g on the sample)
Heat-up rate: 10 ℃/minute
Measurement range: 30～300 ℃
Measure atmosphere gas: nitrogen (flow 50ml/ branch)
Measure sample: the resin after solidifying, the distortion when solidifying in order to make relaxes, and is used in 1 minute sample of 300 ℃ of heating.
Specimen shape: wide 5mm * thick 50 μ m
Measure spacing (distance between chuck): 15mm
[Copper Foil stretch release intensity]
Carry out etching after the tinsel of the metal foil laminated body that obtains sheltered, form the wide conductor layer of 3mm, make to measure and use sample.Then, measure Copper Foil stretch release intensity (stretch release angle 180% according to JIS C6481.In addition, to the said sample pot test (PCT test) of pressurizeing.Test conditions: 121 ℃, 100%RH, 96 hours.To the sample after the PCT test, similarly measure tinsel stretch release intensity with aforesaid operations.
The synthesis example of＜soluble polyimide 〉
Synthesis example 1
In the glass flask of capacity 2000ml, be enclosed in 0.95 normal 1 in the dimethyl formamide (below be called DMF), (Mitsui Chemicals society makes two (3-amino-benzene oxygen) benzene of 3-, be called APB below) and 0.05 normal 3,3 '-dihydroxyl-4, (the Wakayama society that refines makes 4 '-benzidine, be called HAB below), stirring and dissolving in nitrogen atmosphere.
In addition, while use the frozen water cooling solution to stir in the atmosphere in the nitrogen replacement flask, and add 1 normal 4,4 '-(4,4 '-isopropylidene, two phenoxy groups) two Tetra hydro Phthalic anhydrides (GE society makes, and is called IPBP below), restir 3 hours.
Obtain polyamic acid solution thus.Also have, set the consumption of DMF, concentration reaches 30 weight % so that the monomer of APB, HAB and IPBP is packed into.In other words, set the consumption of DMF, make the weight % of polyamic acid contained in the polyamic acid solution that obtains reach 30 weight %.
Above-mentioned polyamic acid solution 300g is moved in the disk that has been coated with fluoro-resin, in vacuum drying oven, condition under 200 ℃ * 3 hours, the pressure of 5mmHg (about 0.007 normal atmosphere, about 5.65hPa) obtains the polyimide resin (a) as soluble polyimide by the decompression heating.
Synthesis example 2
Except adopting two [4-(3-amino-benzene oxygen) phenyl] sulfones (the Wakayama society that refines makes, and is called BAPS-M below) to replace beyond the APB, adopt and same amount of synthesis example 1 and same condition, obtain polyimide resin (b) as soluble polyimide.
Synthesis example 3
Except with 2, two (4-hydroxy phenyl) the propane dibenzoates-3 of 2-, 3 ', 4, (chemistry society in Honshu makes 4 '-tetracarboxylic dianhydride, be called ESDA below) replace beyond the IPBP, adopt and same amount of synthesis example 1 and same condition, obtain polyimide resin (c) as soluble polyimide.
The formulation example of＜polyimide solution (A solution) 〉
[formulation example A-1]
The polyimide resin that obtains in the synthesis example 1 (a) powder 30g is put into the dioxolane of 75g, by stir, dissolving, obtain polyimide solution (A-1) (solid component content (Sc)=30 weight %)
[formulation example A-2]
The polyimide resin that obtains in the synthesis example 2 (b) powder 30g is put into the dioxolane of 70g, by stir, dissolving, obtain polyimide solution (A-2) (SC=30 weight %).
[formulation example A-3]
The polyimide resin that obtains in the synthesis example 3 (c) powder 30g is put into the dioxolane of 70g, by stir, dissolving, obtain polyimide solution (A-3) (SC=30 weight %).
The formulation example of＜cyanate solution (B solution) 〉
[formulation example B-1]
8: 2 mixed solvent 70g to dioxolane and toluene add multi-functional cyanate PRIMASET BADCY (trade(brand)name, the manufacturing of ロ Application ザ society) oligopolymer BA200 (trade(brand)name, ロ Application ザ society makes, monomeric 20～30% in all cyanate ester based is transformed into the oligopolymer of three azine rings) 30g, zinc acetylacetonate (II) 0.08g, temperature ranges stirring at 30～40 ℃ made its dissolving in 2 hours, obtained cyanate solution (B-1) (SC=30%).
[formulation example B-2]
8: 2 mixed solvent 70g to dioxolane and toluene add novolac-type cyanate PRIMASET PT-30 (trade(brand)name, ロ Application ザ society makes, the average repeating unit at novolak position is about 3) 30g, zinc acetylacetonate (II) 0.08g, temperature ranges stirring at 30～40 ℃ made its dissolving in 2 hours, obtained cyanate solution (B-2) (SC=30%).
[formulation example B-3]
8: 2 mixed solvent 700g to dioxolane and toluene add multi-functional cyanate PRIMASET BADCY (trade(brand)name, ロ Application ザ society makes) 300g, acetyl second acetone zinc (II) 0.012g (is 0.012 weight part to multi-functional cyanate 100 weight parts), temperature ranges stirring at 30～40 ℃ made its dissolving in 2 hours, obtained cyanate solution (B-3) (SC=30%).
The formulation example of＜epoxy resin solution (C solution) 〉
[formulation example C-1]
8: 2 mixed solvent 70g to dioxolane and toluene add Resins, epoxy Ai Bikete (エ ピ コ one ト) 1032H60 (trade(brand)name, oiling シ エ Le society makes) 30g, 4,4 '-diamino diphenyl sulfone 9g, (20～30 ℃ temperature ranges) stirred 3 hours under room temperature, make its dissolving, obtain epoxy resin solution (C-1) (SC=30%).
[formulation example C-2]
8: 2 mixed solvent 70g to dioxolane and toluene add Dicyclopentadiene (DCPD) based epoxy resin EXA7200H (trade(brand)name, big Japanese イ Application キ chemical industry (strain) is made) 30g, 4,4 '-diamino diphenyl sulfone 9g, (20～30 ℃ temperature ranges) stirred 3 hours under room temperature, make its dissolving, obtain epoxy resin solution (C-2) (SC=30%).
[formulation example C-3]
8: 2 mixed solvent 70g to dioxolane and toluene add the modified epoxy (trade(brand)name that contains alkoxyl group, waste river chemical industry (strain) is made) 30g, 4,4 '-diamino diphenyl sulfone 9g, (20～30 ℃ temperature ranges) stirred 3 hours under room temperature, make its dissolving, obtain epoxy resin solution (C-3) (SC=30%).
The making example of＜resin sheet 〉
[making example 1]
The polyimide solution that obtains among the formulation example A-1 (A-1) curtain coating on as the surface of 125 μ mPET films of supporter (trade(brand)name セ ラ ピ one Le HP, Japan メ ラ イ ジ Application グ society makes).Then, in hot-air oven respectively at respectively heating 5 minutes under 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃ the temperature, again in 150 ℃ of heat dryings 5 minutes.Then, the sheet that polyimide resin is constituted stretch release from the PET film obtains the single-layer resin sheet that polyimide resin (a) constitutes.The second-order transition temperature of the resin sheet that mensuration obtains.The results are shown in table 1.
[making example 2]
Adopt the polyimide solution (A-2) that obtains among the formulation example A-2, example 1 is same with making, and obtains the single-layer resin sheet that polyimide resin (b) constitutes.The second-order transition temperature of the resin sheet that mensuration obtains.The results are shown in table 1.
[making example 3]
Adopt the polyimide solution (A-3) that obtains among the formulation example A-3, example 1 is same with making, and obtains the single-layer resin sheet that polyimide resin (c) constitutes.The second-order transition temperature of the resin sheet that mensuration obtains.The results are shown in table 1.
Table 1
| Second-order transition temperature (℃) | |
| The polyimide resin of synthesis example 1 | ????160 |
| The polyimide resin of synthesis example 2 | ????215 |
| The polyimide resin of synthesis example 3 | ????165 |
＜embodiment comparative example 〉
At first, as the initial example of compositions of thermosetting resin of the present invention, illustrated only containing the situation of (B) multi-functional cyanate as the thermoset composition.Thereby in the following example 1～5 and comparative example 1,2, in the necessary composition of (A)～(C), containing (A) polyimide resin and (B) example of multi-functional cyanate is as embodiment, other examples in addition as a comparative example.
[embodiment 1]
Cyanate solution (B-1) 20g that obtains among the polyimide solution that obtains among the formulation example A-1 (A-1) 80g and the formulation example B-1 is mixed, be mixed with the solution (resin solution) (with reference to table 2) that contains compositions of thermosetting resin of the present invention.
Secondly, the resin solution that obtains curtain coating on as the thick PET film of 125 μ m of supporter (trade(brand)name セ ラ ピ one Le HP, the manufacturing of Japan メ ラ イ ジ Application グ society) surface.Then, in hot-air oven,, in 150 ℃ of heat dryings 5 minutes, obtain again with 2 layers of resin sheet of PET film as base material respectively at respectively heating 5 minutes under 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃ the temperature.Peel off from this resin sheet and to remove the PET film, obtain the single-layer resin sheet.The thickness of the single-layer resin sheet that this obtains is 50 μ m.
Use the thick rolled copper foil of 18 μ m (trade(brand)name BHY-22B-T, ジ ヤ パ Application エ Na ジ one society makes) to clamp resulting resin sheet, resin surface is contacted with Copper Foil alligatoring face, heating and pressurizing is 1 hour under the condition of 200 ℃ of temperature, pressure 3MPa.Then, in hot-air oven,, compositions of thermosetting resin is solidified, obtain copper foil lamination goods (with the structure of rolled copper foil folder) toward the single-layer resin sheet in 200 ℃ of heat treated 2 hours.
Copper foil lamination goods that employing obtains are measured the Copper Foil stripping strength, in addition, adopt resulting of Copper Foil comprehensively removing these copper foil lamination goods, estimate dielectric characteristics and thermal property.It the results are shown in table 3.
[embodiment 2～5]
Any except polyimide solution A-1 or A-2, cyanate solution B-1～B-3, beyond mixing by the ratio of mixture that provides in the table 2, adopt similarly to Example 1 method and condition, make resin solution, resin sheet and metal foil laminates goods, simultaneously, these are measured, estimate Copper Foil stripping strength, dielectric characteristics and thermal property respectively.It the results are shown in table 3.
[comparative example 1]
Epoxy resin solution (C-1) 20g that obtains among the polyimide solution that obtains among the formulation example A-1 (A-1) 80g and the formulation example C-1 is mixed, be mixed with the solution (resin solution) (with reference to table 2) that contains compositions of thermosetting resin.
Then, the resin solution that obtains curtain coating on as the thick PET film of 125 μ m of supporter (trade(brand)name セ ラ ピ one Le HP, Japan メ ラ イ ジ Application グ society make) surface.Then, in hot-air oven,,, obtain with the PET film that the present invention relates to 2 layers of resin sheet as base material again in 150 ℃ of heat dryings 5 minutes respectively at respectively heating 5 minutes under 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃ the temperature.Peel off from this resin sheet and to remove the PET film, obtain the single-layer resin sheet.The thickness of the resin sheet that this obtains is 50 μ m.
(trade(brand)name BHY-22B-T, ジ ヤ パ Application エ Na ジ one society makes) clamps resulting resin sheet with the thick rolled copper foil of 18 μ m, and resin surface is contacted with Copper Foil alligatoring face, and heating and pressurizing is 1 hour under the condition of 200 ℃ of temperature, pressure 3MPa.Then, again in hot-air oven in 200 ℃ of heat treated 2 hours, compositions of thermosetting resin is solidified, obtain copper foil lamination goods (clamping the structure of single-layer resin sheet with rolled copper foil).
Copper foil lamination goods that employing obtains are measured the Copper Foil stripping strength, in addition, adopt resulting of Copper Foil comprehensively removing these copper foil lamination goods, estimate dielectric characteristics and thermal property.The results are shown in table 3.
[comparative example 2]
Except adopting polyimide solution A-2 replacement polyimide solution A-1, adopt method and the condition same with comparative example 2, make resin solution, resin sheet and metal foil laminates goods, simultaneously these are measured, estimate Copper Foil stripping strength, dielectric characteristics and thermal property respectively.It the results are shown in table 3.
Table 2
| The kind of A solution | The kind of B solution | A solution: B solution (weight ratio) | |
| Embodiment 1 | ????A-1 | ????B-1 | ????80∶20 |
| Embodiment 2 | ????A-1 | ????B-1 | ????30∶70 |
| Embodiment 3 | ????A-1 | ????B-2 | ????80∶20 |
| Embodiment 4 | ????A-2 | ????B-1 | ????80∶20 |
| Embodiment 5 | ????A-2 | ????B-3 | ????60∶40 |
| Comparative example 1 | ????A-1 | ????C-1 | ????80∶20 |
| Comparative example 2 | ????A-2 | ????C-1 | ????80∶20 |
Table 3
| Bonding strength (N/cm) | Dielectric characteristics (specific inductivity/dielectric loss tangent) | Thermal expansivity (ppm) | |||
| ?3GHz | ?5GHz | ?10GHz | |||
| Embodiment 1 | ????9 | ?2.9/0.004 | ?2.9/0.004 | ?2.9/0.005 | ????105 |
| Embodiment 2 | ????7 | ?3.0/0.009 | ?2.8/0.009 | ?2.8/0.010 | ????88 |
| Embodiment 3 | ????10 | ?3.0/0.005 | ?2.9/0.005 | ?2.9/0.005 | ????120 |
| Embodiment 4 | ????10 | ?2.9/0.007 | ?2.9/0.007 | ?2.9/0.006 | ????77 |
| Embodiment 5 | ????9 | ?2.9/0.008 | ?2.8/0.009 | ?2.8/0.009 | ????124 |
| Comparative example 1 | ????12 | ?3.3/0.012 | ?3.2/0.012 | ?3.2/0.013 | ????490 |
| Comparative example 2 | ????11 | ?3.2/0.013 | ?3.2/0.013 | ?3.1/0.014 | ????401 |
As mentioned above, even contain the occasion of (B) multi-functional cyanate, also can show very good various characteristics as the thermoset composition.Opposite at this, as (C) epoxy resin, in the comparative example that adopts the Resins, epoxy that uses before this, its thermal expansivity raises.
Secondly, as compositions of thermosetting resin following Example of the present invention, be only to contain (B) multi-functional cyanate, in addition as the thermoset composition, in order to obtain the well balanced of anti-PCT and processibility, and the situation that these proportionings are controlled in the specific scope is illustrated.Thereby, in the following example 6～12 and comparative example 3,4, contain (A) polyimide resin and reach (B) multi-functional cyanate, and show in PCT test back result that cohesive strength is high as embodiment, even and other examples in addition comprise within the scope of the invention also as a comparative example.
[embodiment 6]
Multi-functional cyanate solution (B-1) 10g that obtains among the polyimide solution that obtains among the formulation example A-1 (A-1) 90g and the formulation example B-1 is mixed, be mixed with the resin solution (with reference to table 4) that contains compositions of thermosetting resin of the present invention.
Secondly, the resin solution that obtains curtain coating on as the thick PET film of 125 μ m of supporter (trade(brand)name セ ラ ピ one Le HP, the manufacturing of Japan メ ラ イ ジ Application グ society) surface.Then, in hot-air oven,, in 150 ℃ of heat dryings 5 minutes, obtain again with 2 layers of resin sheet of PET film as base material respectively at respectively heating 5 minutes under 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃ the temperature.Peel off from this resin sheet and to remove the PET film, obtain the single-layer resin sheet.The thickness of this resin sheet that obtains is 50 μ m.
(trade(brand)name BHY-22B-T, ジ ヤ パ Application エ Na ジ one society makes) clamps resulting resin sheet with the thick rolled copper foil of 18 μ m, and resin surface is contacted with Copper Foil alligatoring face, and heating and pressurizing is 1 hour under the condition of 200 ℃ of temperature, pressure 3MPa.Then, again in hot-air oven in 200 ℃ of heat treated 2 hours, resin combination is solidified, obtain copper foil lamination goods (with the structure of rolled copper foil clamping single-layer resin sheet).
Copper foil lamination goods that employing obtains are measured the Copper Foil stripping strength, in addition, adopt resulting of Copper Foil comprehensively removing these copper foil lamination goods, estimate dielectric characteristics and thermal property.It the results are shown in table 5.
[embodiment 7～12]
Except any, cyanate solution B-1 of polyimide solution A-1～A-3 or B-2 and other compositions are mixed by the proportioning of table 4, adopt similarly to Example 6 method and condition, make resin solution, resin sheet and metal foil laminates goods, simultaneously, these are measured, estimate Copper Foil stripping strength, dielectric characteristics and thermal property respectively.It the results are shown in table 5.
[comparative example 3]
Except polyimide solution (A-1) 80g and cyanate solution (B-1) 20g are mixed, adopt similarly to Example 1 method and condition, make resin solution, resin sheet and metal foil laminates goods, simultaneously, these are measured, estimate Copper Foil stripping strength, dielectric characteristics respectively.It the results are shown in table 5.
[comparative example 4]
Except polyimide solution (A-1) 98g and cyanate solution (B-1) 2g are mixed, adopt method and the condition same with comparative example 3, make resin solution, resin sheet and metal foil laminates goods, simultaneously, these are measured, estimate Copper Foil stripping strength, dielectric characteristics respectively.It the results are shown in table 5.
Table 4
| The kind of A solution | The kind of B solution | A solution: B solution (weight ratio) | Curing catalysts (parts by weight/(B) composition) | |
| Embodiment 6 | ????A-1 | ????B-1 | ????90∶10 | ????0 |
| Embodiment 7 | ????A-1 | ????B-1 | ????90∶10 | ????0.003 |
| Embodiment 8 | ????A-1 | ????B-2 | ????90∶10 | ????0 |
| Embodiment 9 | ????A-2 | ????B-1 | ????90∶10 | ????0 |
| Embodiment 10 | ????A-3 | ????B-1 | ????90∶10 | ????0 |
| Embodiment 11 | ????A-1 | ????B-1 | ????86∶14 | ????0 |
| Embodiment 12 | ????A-1 | ????B-1 | ????94∶6 | ????0 |
| Comparative example 3 | ????A-1 | ????B-1 | ????80∶20 | ????0 |
| Comparative example 4 | ????A-1 | ????B-1 | ????98∶2 | ????0 |
Table 5
| Cohesive strength [before the PCT] (N/cm) | Cohesive strength [behind the PCT] (N/cm) | Dielectric characteristics (specific inductivity/dielectric loss tangent) | |||
| ??3GHz | ?5GHz | ??10GHz | |||
| Embodiment 6 | ????14 | ????9 | ??2.8/0.004 | ?2.8/0.004 | ??2.7/0.005 |
| Embodiment 7 | ????14 | ????10 | ??2.8/0.004 | ?2.8/0.004 | ??2.8/0.005 |
| Embodiment 8 | ????13 | ????9 | ??2.9/0.005 | ?2.9/0.005 | ??2.9/0.006 |
| Embodiment 9 | ????10 | ????7 | ??2.9/0.006 | ?2.9/0.006 | ??2.9/0.007 |
| Embodiment 10 | ????13 | ????9 | ??2.7/0.005 | ?2.7/0.005 | ??2.7/0.006 |
| Embodiment 11 | ????16 | ????6 | ??2.9/0.006 | ?2.9/0.007 | ??2.8/0.007 |
| Embodiment 12 | ????12 | ????11 | ??2.9/0.007 | ?2.9/0.007 | ??2.9/0.007 |
| Comparative example 3 | ????9 | ????3 | ??2.9/0.004 | ?2.9/0.004 | ??2.9/0.005 |
| Comparative example 4 | ????2 | ????2 | ??2.7/0.004 | ?2.7/0.004 | ??2.6/0.004 |
As mentioned above, (A) polyimide resin and (B) the mixed of multi-functional cyanate contain than (A/B), in the time of by weight in 95/5～85/15 scope, Copper Foil stripping strength after the PCT test keeps high value, and beyond the above-mentioned scope time, the Copper Foil stripping strength after the PCT test obviously descends.
Secondly, as the following Example of compositions of thermosetting resin of the present invention, be that the situation that will only contain (C) epoxy resin as the thermoset composition is illustrated.Thereby, in the following example 13～16 and the comparative example 5～7, contain (A) polyimide resin and (C) epoxy resin, and show high cohesive strength result as embodiment, and other example is as a comparative example.
[embodiment 13]
The polyimide resin that obtains in the synthesis example 1 (a) 35g, Dicyclopentadiene (DCPD) based epoxy resin EXA7200 (trade(brand)name, big Japanese イ Application キ chemical industry (strain) is made) 15g and be dissolved in the dioxolane as the 2-ethyl-4-methylimidazole 0.015g of curing catalyst, obtain resin solution.
Secondly, the resin solution that obtains curtain coating on as the thick PET film of 125 μ m of supporter (trade(brand)name セ ラ ピ one Le HP, the manufacturing of Japan メ ラ イ ジ Application グ society) surface.Then, in hot-air oven,, in 150 ℃ of heat dryings 5 minutes, obtain again with 2 layers of resin sheet of PET film as base material respectively at respectively heating 5 minutes under 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃ the temperature.Peel off from this resin sheet and to remove the PET film, obtain the single-layer resin sheet.The thickness of this single-layer resin sheet that obtains is 50 μ m.
(trade(brand)name BHY-22B-T, ジ ヤ パ Application エ Na ジ one society makes) clamps resulting resin sheet with the thick rolled copper foil of 18 μ m, and resin surface is contacted with Copper Foil alligatoring face, and heating and pressurizing is 1 hour under the condition of 200 ℃ of temperature, pressure 3MPa.Then, again in hot-air oven in 200 ℃ of heat treated 2 hours, compositions of thermosetting resin is solidified, obtain copper foil lamination goods (clamping the structure of single-layer resin sheet with rolled copper foil).
The metal laminated goods that employing obtains are measured the Copper Foil stripping strength, in addition, adopt resulting of Copper Foil comprehensively removing these metal laminated goods, estimate dielectric characteristics and thermal property.It the results are shown in table 6.
[embodiment 14]
The polyimide resin that obtains in the synthesis example 2 (b) 35g, Dicyclopentadiene (DCPD) based epoxy resin EXA7200 (trade(brand)name, big Japanese イ Application キ chemical industry (strain) is made) 15g and be dissolved in the dioxolane as the 2-ethyl-4-methylimidazole 0.015g of curing catalyst, obtain resin solution.
The resin solution that obtains, adopt similarly to Example 13 method and condition, make resin solution, resin sheet and metal foil laminates goods, simultaneously, these are measured, estimate Copper Foil stripping strength, dielectric characteristics respectively.It the results are shown in table 6.
[embodiment 15]
The polyimide resin that obtains in the synthesis example 1 (a) 40g, contain the silane-modified epoxy resin コ Application パ セ ラ Application E103 (trade(brand)name of alkoxyl group, waste river chemical industry (strain) is made) 10g and be dissolved in the dioxolane as the 2-ethyl-4-methylimidazole 0.01g of curing catalyst, obtain resin solution.
The resin solution that obtains, adopt similarly to Example 13 method and condition, make resin solution, resin sheet and metal foil laminates goods, simultaneously, these are measured, estimate Copper Foil stripping strength, dielectric characteristics respectively.It the results are shown in table 6.
[embodiment 16]
The polyimide resin that obtains in the synthesis example 1 (a) 30g, Dicyclopentadiene (DCPD) based epoxy resin EPICLON EXA7200H (trade(brand)name, big Japanese イ Application キ chemical industry (strain) is made) 20g and naphthalene based epoxy resin EPICLON EXA-4700 (trade(brand)name, big Japanese イ Application キ chemical industry (strain) manufacturing) 1g is dissolved in the dioxolane, obtains resin solution.
The resin solution that obtains, adopt similarly to Example 13 method and condition, make resin solution, resin sheet and metal foil laminates goods, simultaneously, these are measured, estimate Copper Foil stripping strength, dielectric characteristics respectively.It the results are shown in table 6.
[comparative example 5]
The polyimide resin that obtains in the synthesis example 1 (a) 30g, dihydroxyphenyl propane based epoxy resin エ ピ コ one ト 828 (trade(brand)names, oiling シ エ Le (strain) is made) 20g and be dissolved in the dioxolane as the 2-ethyl-4-methylimidazole 0.01g of curing catalyst, obtain resin solution.
The resin solution that obtains, adopt similarly to Example 13 method and condition, make resin solution, resin sheet and metal foil laminates goods, simultaneously, these are measured, estimate Copper Foil stripping strength, dielectric characteristics respectively.It the results are shown in table 6.
[comparative example 6]
The polyimide resin that obtains in the synthesis example 2 (b) 40g, novolak based epoxy resin エ ピ コ one ト 1032H60 (trade(brand)name, oiling シ エ Le (strain) is made) 10g and be dissolved in the dioxolane as the 2-ethyl-4-methylimidazole 0.01g of curing catalyst, obtain resin solution.
The resin solution that obtains, adopt similarly to Example 13 method and condition, make resin solution, resin sheet and metal foil laminates goods, simultaneously, these are measured, estimate Copper Foil stripping strength, dielectric characteristics respectively.It the results are shown in table 6.
[comparative example 7]
The nylon プ ラ ボ Application De M1276 (trade(brand)name that copolymerization is obtained, the manufacturing of Japan リ Le サ Application society) 35g, Dicyclopentadiene (DCPD) based epoxy resin EPICLON EXA7200H (trade(brand)name, big Japanese イ Application キ chemical industry (strain) is made) 15g, be dissolved in the dioxolane as the diamino diphenyl sulfone 1g of solidifying agent and as the 2-ethyl-4-methylimidazole 0.015g of curing catalyst, obtain resin solution.
The resin solution that obtains, adopt similarly to Example 13 method and condition, make resin solution, resin sheet and metal foil laminates goods, simultaneously, these are measured, estimate Copper Foil stripping strength, dielectric characteristics respectively.It the results are shown in table 6.
Table 6
| Cohesive strength [20 ℃] (N/cm) | Cohesive strength [150 ℃] (N/cm) | Dielectric characteristics (specific inductivity/dielectric loss tangent) | |||
| ?3GHz | ?5GHz | ?10GHz | |||
| Embodiment 13 | ????11 | ????8 | ?3.1/0.014 | ?3.1/0.013 | ?3.0/0.014 |
| Embodiment 14 | ????11 | ????8 | ?3.2/0.012 | ?3.2/0.012 | ?3.2/0.012 |
| Embodiment 15 | ????10 | ????7 | ?3.0/0.010 | ?3.0/0.010 | ?2.9/0.011 |
| Embodiment 16 | ????10 | ????7 | ?3.0/0.009 | ?3.0/0.009 | ?3.0/0.009 |
| Comparative example 5 | ????11 | ????8 | ?3.4/0.022 | ?3.4/0.022 | ?3.3/0.024 |
| Comparative example 6 | ????10 | ????9 | ?3.2/0.018 | ?3.2/0.018 | ?3.2/0.019 |
| Comparative example 7 | ????12 | ????1 | ?3.3/0.020 | ?3.3/0.020 | ?3.3/0.020 |
As mentioned above, (A) polyimide resin and (B) the mixed of multi-functional cyanate contain than (A/B), in the time of by weight in 95/5～85/15 scope, Copper Foil stripping strength after the PCT test keeps high value, and beyond the above-mentioned scope time, the Copper Foil stripping strength after the PCT test obviously descends.
As mentioned above, when the suitable Resins, epoxy that contains as above-mentioned (C) epoxy resin of thermoset composition, can show very good various rerum naturas.In contrast, as (C) epoxy resin, in the comparative example that uses the Resins, epoxy that in the past adopts, cohesive strength is insufficient, can not get low dielectric characteristics.
Secondly, as compositions of thermosetting resin following Example of the present invention, enumerate contain as (B) multi-functional cyanate of thermoset composition and (C) both examples of epoxy resin be illustrated.Thereby, in the following example 17～23 and the comparing class example 8～13, contain (A) polyimide resin, (B) multi-functional cyanate and (C) epoxy resin as embodiment, even and other example within the scope of the present invention also as a comparative example.
[embodiment 17]
Cyanate solution (B-1) 15g that obtains among the polyimide solution that obtains among the formulation example A-1 (A-1) 80g and the formulation example B-1 and, epoxy resin solution (C-1) 5g that obtains among the formulation example C-1 mixed, and is mixed with the solution (resin solution) (with reference to table 7) that contains compositions of thermosetting resin.
Secondly, the resin solution that obtains curtain coating on as the thick PET film of 125 μ m of supporter (trade(brand)name セ ラ ピ one Le HP, the manufacturing of Japan メ ラ イ ジ Application グ society) surface.Then, in hot-air oven,, in 150 ℃ of heat dryings 5 minutes, obtain again with 2 layers of resin sheet of PET film as base material respectively at respectively heating 5 minutes under 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃ the temperature.Peel off from this resin sheet and to remove the PET film, obtain the single-layer resin sheet.The thickness of this resin sheet that obtains is 50 μ m.
(trade(brand)name BHY-22B-T, ジ ヤ パ Application エ Na ジ one society makes) clamps resulting resin sheet with the thick rolled copper foil of 18 μ m, and resin surface is contacted with Copper Foil alligatoring face, and heating and pressurizing is 1 hour under the condition of 200 ℃ of temperature, pressure 3MPa.Then, again in hot-air oven in 200 ℃ of heat treated 2 hours, compositions of thermosetting resin is solidified, obtain copper foil lamination goods (clamping the structure of single-layer resin sheet with rolled copper foil).
Copper foil lamination goods that employing obtains are measured the Copper Foil stripping strength, in addition, adopt resulting of Copper Foil comprehensively removing these copper foil lamination goods, estimate dielectric characteristics and thermal property.It the results are shown in table 8.
[embodiment 18～23]
Any except any, cyanate solution B-1 of polyimide solution A-1～A-3 or B-2, epoxy resin solution C-1～C-3, beyond mixing by the proportioning that provides in the table 7, adopt similarly to Example 17 method and condition, make resin solution, resin sheet and metal foil laminates goods, simultaneously, these are measured, estimate Copper Foil stripping strength, dielectric characteristics and thermal property respectively.It the results are shown in table 8.
[comparative example 8]
Beyond multi-functional cyanate solution (B-1) 20g that obtains among the polyimide solution that obtains in the formulation example 1 (A-1) 80g and the formulation example B-1 mixed, adopt similarly to Example 17 method and condition, make resin solution, resin sheet and metal foil laminates goods, these are measured, estimate Copper Foil stripping strength, dielectric characteristics and thermal property respectively.It the results are shown in table 8.
[comparative example 9～11]
Except polyimide solution A-1 or A-2, cyanate solution B-1 or B-2, beyond being mixed by the proportioning of table 7, adopt similarly to Example 17 method and condition, make resin solution, resin sheet and metal foil laminates goods, simultaneously these are measured, estimate Copper Foil stripping strength, dielectric characteristics and thermal property respectively.It the results are shown in table 8.
[comparative example 12]
The polyimide solution that obtains among the formulation example A-1 (A-1) 80g and, epoxy resin solution (C-3) 20g that obtains among the formulation example C-3 mixed, and is mixed with the solution (resin solution) (with reference to table 7) that contains compositions of thermosetting resin of the present invention.
Secondly, the resin solution that obtains curtain coating on as the thick PET film of 125 μ m of supporter (trade(brand)name セ ラ ピ one Le HP, the manufacturing of Japan メ ラ イ ジ Application グ society) surface.Then, in hot-air oven,, in 150 ℃ of heat dryings 5 minutes, obtain again with 2 layers of resin sheet of PET film as base material respectively at respectively heating 5 minutes under 60 ℃, 80 ℃, 100 ℃, 120 ℃, 140 ℃ the temperature.Peel off from this resin sheet and to remove the PET film, obtain the single-layer resin sheet.The thickness of this resin sheet that obtains is 50 μ m.
(trade(brand)name BHY-22B-T, ジ ヤ パ Application エ Na ジ one society makes) clamps resulting resin sheet with the thick rolled copper foil of 18 μ m, and resin surface is contacted with Copper Foil alligatoring face, and heating and pressurizing is 1 hour under the condition of 200 ℃ of temperature, pressure 3MPa.Then, again in hot-air oven in 200 ℃ of following heat treated 2 hours, compositions of thermosetting resin is solidified, obtain copper foil lamination goods (clamping the structure of single-layer resin sheet with rolled copper foil).
Copper foil lamination goods that employing obtains are measured the Copper Foil stripping strength, in addition, adopt resulting of Copper Foil comprehensively removing these copper foil lamination goods, estimate dielectric characteristics and thermal property.It the results are shown in table 8.
[comparative example 13]
Except replace polyimide solution A-1 with polyimide solution A-2, adopt method and the condition same with comparative example 13, make resin solution, resin sheet and metal foil laminates goods, these are measured, estimate Copper Foil stripping strength, dielectric characteristics and thermal property respectively.It the results are shown in table 8.
Table 7
| The kind of A solution | The kind of B solution | The kind of C solution | A solution: B solution: C solution (weight ratio) | |
| Embodiment 17 | ????A-1 | ????B-1 | ????C-1 | ????80∶15∶5 |
| Embodiment 18 | ????A-1 | ????B-1 | ????C-1 | ????60∶30∶10 |
| Embodiment 19 | ????A-1 | ????B-2 | ????C-1 | ????80∶15∶5 |
| Embodiment 20 | ????A-2 | ????B-1 | ????C-1 | ????80∶15∶5 |
| Embodiment 21 | ????A-3 | ????B-1 | ????C-1 | ????80∶15∶5 |
| Embodiment 22 | ????A-1 | ????B-1 | ????C-2 | ????80∶15∶5 |
| Embodiment 23 | ????A-1 | ????B-1 | ????C-3 | ????80∶15∶5 |
| Comparative example 8 | ????A-1 | ????B-1 | ????- | ????80∶20∶0 |
| Comparative example 9 | ????A-1 | ????B-1 | ????- | ????60∶40∶0 |
| Comparative example 10 | ????A-1 | ????B-2 | ????- | ????80∶20∶0 |
| Comparative example 11 | ????A-2 | ????B-1 | ????- | ????80∶20∶0 |
| Comparative example 12 | ????A-1 | ????- | ????C-1 | ????80∶0∶20 |
| Comparative example 13 | ????A-2 | ????- | ????C-1 | ????80∶0∶20 |
Table 8
| Cohesive strength [normality] (N/cm) | Cohesive strength [behind the PCT] (N/cm) | Dielectric characteristics (specific inductivity/dielectric loss tangent) | Thermal expansivity (ppm) | |||
| ?3GHz | ?5GHz | ?10GHz | ||||
| Embodiment 17 | ????10 | ????7 | ?3.0/0.006 | ?3.0/0.006 | ?3.0/0.006 | ????120 |
| Embodiment 18 | ????8 | ????6 | ?3.1/0.010 | ?3.1/0.011 | ?3.1/0.010 | ????95 |
| Embodiment 19 | ????10 | ????8 | ?3.0/0.006 | ?3.1/0.007 | ?3.0/0.006 | ????136 |
| Embodiment 20 | ????10 | ????7 | ?3.0/0.008 | ?3.0/0.008 | ?3.0/0.008 | ????85 |
| Embodiment 21 | ????10 | ????8 | ?2.9/0.009 | ?2.9/0.009 | ?2.8/0.010 | ????90 |
| Embodiment 22 | ????9 | ????8 | ?2.9/0.007 | ?2.9/0.007 | ?2.9/0.007 | ????114 |
| Embodiment 23 | ????12 | ????9 | ?2.8/0.007 | ?2.8/0.007 | ?2.8/0.007 | ????102 |
| Comparative example 8 | ????9 | ????3 | ?2.9/0.004 | ?2.9/0.004 | ?2.9/0.005 | ????105 |
| Comparative example 9 | ????7 | ????2 | ?3.0/0.009 | ?2.8/0.009 | ?2.8/0.010 | ????88 |
| Comparative example 10 | ????10 | ????3 | ?3.0/0.005 | ?2.9/0.005 | ?2.9/0.005 | ????120 |
| Comparative example 11 | ????10 | ????3 | ?2.9/0.007 | ?2.9/0.007 | ?2.9/0.006 | ????77 |
| Comparative example 12 | ????12 | ????10 | ?3.3/0.012 | ?3.2/0.012 | ?3.2/0.013 | ????490 |
| Comparative example 13 | ????11 | ????8 | ?3.3/0.013 | ?3.2/0.013 | ?3.1/0.014 | ????401 |
As mentioned above, even, still can show very good various rerum naturas contain (B) multi-functional cyanate and (C) Resins, epoxy time-like as the thermoset composition.In contrast, only contain in any a kind of comparative example as the thermoset composition in use, it is insufficient that cohesive strength becomes sometimes.
As mentioned above, compositions of thermosetting resin of the present invention is to contain (A) polyimide resin, (B) multi-functional cyanate and/or (C) at least a kind of epoxy resin, and according to purposes, contains also that above-mentioned (D) other compositions constitute.
More particularly, in the present invention,, be and with (B) multi-functional cyanate and (C) at least a kind in the epoxy resin as being the thermoset composition that cooperates in (A) polyimide resin of main component.
At this moment, as (A) polyimide resin, the soluble polyimide that preferably adopts acid dianhydride with ehter bond and diamine reactant with general formula (1) expression to obtain.In addition, as (B) multi-functional cyanate, can adopt monomer and/or its oligopolymer with above-mentioned general formula (6) expression, as (C) epoxy resin, preferably can adopt Resins, epoxy and/or contain the silane-modified Resins, epoxy (suitable Resins, epoxy) of alkoxyl group with Dicyclopentadiene (DCPD) skeleton.
In addition, for (A) polyimide resin, when the multi-functional cyanate (B) that cooperates as one of thermoset composition, each use level (blended amount) is transferred in the scope of regulation.These (A) and each composition ratio of mixture (B) count 95/5～85/15th by weight, and be preferred.At this moment, in above-mentioned thermoplastic resin composition, solidify the cohesive force of back and Copper Foil, before and after PCT handled, it was preferred reaching the above person of 5N/cm and 5N/cm, and (A) second-order transition temperature of polyimide resin is preferred person below 250 ℃ and 250 ℃.In addition, to (C) composition also with specific weight ratio in addition the mixer be preferred.
In other words, as long as compositions of thermosetting resin of the present invention contains (A) polyimide resin, (B) multi-functional cyanate and/or (C) any a kind of 3 kinds of compositions of epoxy resin, but as concrete composition, preferably: as (A), with the soluble polyimide of general formula (1) expression; As (B), with the multi-functional cyanate of general formula (6) expression; As (C), with at least a kind in the Resins, epoxy of general formula (8), (9) and (10) expression, and in these 3 kinds of concrete compositions, it is preferred containing 2 kinds at least.
In the above-described configuration, at first,, not only special mixing arranged with (B) multi-functional cyanate if adopt above-mentioned soluble polyimide as (A) polyimide resin, and, can be good in wide blending ratio scope mix.Therefore, when adopting compositions of thermosetting resin of the present invention, can not reduce (A) polyimide resin excellent dielectric characteristic (improving specific inductivity and dielectric loss tangent), and improve various rerum naturas such as processibility, and make all rerum naturas such as thermotolerance good yet.Yet compositions of thermosetting resin of the present invention even compare with original thermoplastic polyimide resin class blending matrix material, because second-order transition temperature is lower, when bonding adherend, can carry out bonding in lower temperature.Therefore, paste processibility that adds man-hour and the property handled etc. and also become good.
In addition, as above-mentioned (B) multi-functional cyanate,, can be mixed in (A) polyimide resin with sufficient amount with (C) epoxy resin if adopt above-mentioned monomer and/or its oligopolymer.Therefore, if (B) multi-functional cyanate content is abundant, compare with the original epoxy resin matrix material and the blending matrix material of sneaking into the polyimide/epoxy resin so, compositions of thermosetting resin of the present invention, various characteristicses such as its dielectric characteristics, cohesiveness, processibility, thermotolerance reach good balance.Particularly, the processibility of resulting compositions of thermosetting resin, pasting the processibility that adds man-hour at employing pressing unit and laminated device etc. especially can be improved.In addition, when processibility improves, can suppress the decline of (A) polyimide resin excellent dielectric characteristic, anti-PCT also can obtain performance.
In addition, as above-mentioned (C) epoxy resin, if adopt described suitable Resins, epoxy, then mixing this Resins, epoxy makes reach sufficient amount in polyimide resin, even the processibility of this compositions of thermosetting resin improves, then the reduction of polyimide resin excellent dielectric characteristic also can be inhibited, or close-burningly environment resistantly also becomes good.And, if (C) epoxy resin content is abundant, compositions of thermosetting resin of the present invention, even be processed into also can bring into play under the flaky state close-burning environment resistant.
In addition, as mentioned above, if set the ratio of mixture of (A), (B), (C) each composition, then not only can improve anti-PCT, and processibility can improve also, the processibility when particularly adopting pressing unit or laminated device etc. to fit also can be brought into play.
Also have, in for enforcement preferred plan project of the present invention, more particular embodiment or embodiment, as long as understand technology contents of the present invention, and should not do narrow sense be interpreted as only be defined as these embodiment, in the scope of spirit of the present invention and following claim, certainly do various changes and implemented.
Industrial applicibility
As mentioned above, compositions of thermosetting resin of the present invention, the laminated product and the circuit substrate that adopt said composition to consist of, good in dielectric property, processability, heat resistance and the caking property of GHz wave band, in addition, and caking property, particularly anti-PCT is also good.
The result is, in the present invention, the problem that produces in the time of can fully eliminating the binding material that adopts above-mentioned original fusion, as laminated products such as FPC or harness substrates, go for requiring the manufacturing of the circuit substrate of the low-dielectrics such as heat resistance, low-k, low-dielectric loss tangent.
Therefore, the present invention, except the polymer chemistry industry of making various resins or resin combination, can be applied to make the applied chemistry industry of binding material or resin sheet, the laminated product etc. of fusion, in addition, electric, the electronic manufacturing fields such as FPC and harness substrate, or utilize them to make field electric, electronic instrument and also can utilize.
Claims (21)
1. compositions of thermosetting resin, said composition contain (A) polyimide resin and, as (B) multi-functional cyanate of thermoset composition and (C) at least a kind in the epoxy resin;
As above-mentioned (A) polyimide resin, be to make at least with following general formula (1):
(in the formula, V represents to be selected from-O-,-CO-,-divalent group in O-T-O-and the COO-T-OCO-group, T represents the divalent organic group) at least a kind of acid dianhydride of expression and the soluble polyimide that the reaction of two amines obtains.
2. according to the compositions of thermosetting resin described in the claim 1, wherein, above-mentioned two amines are at least a kind of two amines with following general formula (4) expression:
(in the formula, Y
1And Y
2Independently of one another expression-C (=O)-,-SO
2-,-O-,-S-,-(CH
2)
m-,-NHCO-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=O) O-or singly-bound (directly key), R
1, R
2And R
3Independently represent the alkyl of hydrogen atom, Halogen group or carbonatoms 1～5 respectively, m and n represent 1～5 integer).
3. according to the compositions of thermosetting resin described in the claim 2, wherein, above-mentioned two amines are two amines with following general formula (5) expression:
(in the formula, Y
3And Y
4Respectively independently expression-C (=O)-,-SO
2-,-O-,-S-,-(CH
2)
m-,-NHCO-,-C (CH
3)
2-,-C (CF
3)
2-,-C (=O) O-or singly-bound (directly in conjunction with), R
4, R
5And R
6Independently represent the alkyl of hydrogen atom, Halogen group or carbonatoms 1～4 respectively, m and n represent 1～5 integer).
4. according to the compositions of thermosetting resin described in the claim 2, wherein,, contain a kind of diamines at least with hydroxyl and/or carboxyl as above-mentioned two amines.
5. according to the compositions of thermosetting resin described in the claim 1, wherein, in the acid dianhydride with above-mentioned general formula (1) expression, the T in this general formula (1) is with following group (2):
The organic group of expression, or with following general formula (3):
(in the formula, Z is for being selected from-C
QH
2Q-,-C (=O)-,-SO
2-,-O-and-divalent group in the S-group, Q is 1～5 integer) organic group of expression.
6. according to the compositions of thermosetting resin described in the claim 1, wherein, as the second-order transition temperature of the soluble polyimide of (A) polyimide resin below 250 ℃ and 250 ℃.
7. according to the compositions of thermosetting resin described in the claim 1, wherein,, be from following general formula (6) as above-mentioned (B) multi-functional cyanate:
(in the formula, R
7Expression from divalent organic group with at least a kind on singly-bound, aromatic nucleus, aliphatics ring ,-CH
2-,-C (CH
3)
2-,-C (CF
3)
2-,-CH (CH
3)-,-CH (CF
3)-,-SO
2-,-S-,-O-, selection, R
8, R
9Identical or different respectively, and be selected from-H ,-CH
3,-CF
3, o represents 0～7 integer, p, q are identical or different respectively, and represent 0～3 integer)
Multi-functional cyanate of selecting in the compound of expression and/or at least a kind of from its oligopolymer, selecting.
8. according to the compositions of thermosetting resin described in the claim 7, wherein, above-mentioned (B) multi-functional cyanate is at least a kind that selects from the compound of following group (7) expression:
(in the formula, r and t represent 0～5 integer).
9. according to the compositions of thermosetting resin described in the claim 1, wherein, as above-mentioned (C) epoxy resin, adopt from reaching the Resins, epoxy of (10) expression and/or contain at least a kind of Resins, epoxy selecting the silane-modified Resins, epoxy of alkoxyl group with following general formula (8), (9):
(above-mentioned various in, G represents the organic group represented with following structural:
I, j, k represent 0～5 integer, R respectively independently
10, R
11, R
12, R
13The alkyl of representing hydrogen atom or carbonatoms 1～4 respectively independently).
10. according to the compositions of thermosetting resin described in the claim 1, wherein, C
AWeight, the C of total composition of expression (A) polyimide resin
BDuring the weight of total composition of expression (B) multi-functional cyanate, above-mentioned (A) polyimide resin and (B) ratio of mixture of multi-functional cyanate in following ranges:
C
A∶C
B＝20∶80～90∶10
11. according to the compositions of thermosetting resin described in the claim 1, wherein, C
AWeight, the C of total composition of expression (A) polyimide resin
BDuring the weight of total composition of expression (B) multi-functional cyanate, above-mentioned (A) polyimide resin and (B) ratio of mixture of multi-functional cyanate in following ranges:
C
A∶C
B＝95∶5～85∶15
12. according to the compositions of thermosetting resin described in the claim 1, wherein, C
AWeight, the C of total composition of expression (A) polyimide resin
CDuring the weight of total composition of expression (C) epoxy resin class, above-mentioned (A) polyimide resin and (C) ratio of mixture of epoxy resin class in following ranges:
C
A∶C
C＝50∶50～99∶1
13. according to the compositions of thermosetting resin described in the claim 1, wherein, C
AWeight, the C of total composition of expression (A) polyimide resin
BWeight, the C of total composition of expression (B) multi-functional cyanate
CDuring the weight of total composition of expression (C) epoxy resin class, above-mentioned (A) polyimide resin, (B) multi-functional cyanate and (C) each ratio of components of epoxy resin class in following ranges:
C
A/(C
A+C
B+C
C)＝0.5～0.96
C
B/(C
A+C
B+C
C)＝0.02～0.48
C
C/(C
A+C
B+C
C)＝0.002～0.48
14., wherein, also contain at least a kind in promotion (B) multi-functional cyanate solidified curing catalysts and promotion (C) the epoxy resin solidified solidifying agent according to the compositions of thermosetting resin described in the claim 1.
15. according to the compositions of thermosetting resin described in the claim 14, wherein, as promoting above-mentioned (B) multi-functional cyanate solidified curing catalysts, use at least a kind that is selected from zinc acetylacetonate (II), zinc naphthenate, acetylacetone cobalt (II), acetylacetone cobalt (III), cobalt naphthenate, acetylacetone copper (II), the copper naphthenate.
16. according to the compositions of thermosetting resin described in the claim 14, wherein, the curing catalyst that contains promotion (C) epoxy resin solidified solidifying agent and promote to react with (C) epoxy resin.
17. according to the compositions of thermosetting resin described in the claim 1, wherein, after heating under 200 ℃～250 ℃ the temperature condition made it solidify in 1 hour～5 hours, satisfy one of following condition at least: condition 1, below the specific inductivity 3.0 and 3.0, below the dielectric loss tangent 0.01 and 0.01; Condition 2, before and after PCT handles, with the cohesive force of Copper Foil any a kind all at 5N/cm with more than the 5N/cm.
18. according to the compositions of thermosetting resin described in the claim 17, wherein, also have, in above-mentioned condition 1, specific inductivity below 3.2 and 3.2, dielectric loss tangent is below 0.012 and 0.012.
19. a compositions of thermosetting resin, said composition contains (A) polyimide resin and as (B) multi-functional cyanate of thermoset composition and (C) at least a kind in the epoxy resin;
As above-mentioned (B) multi-functional cyanate, use from following general formula (6):
(in the formula, R
7Expression from divalent organic group with at least a kind on singly-bound, aromatic nucleus, aliphatics ring ,-CH
2-,-C (CH
3)
2-,-C (CF
3)
2-,-CH (CH
3)-,-CH (CF
3)-,-SO
2-,-S-,-O-, middle selection, R
8, R
9Identical or different respectively, be selected from-H ,-CH
3,-CF
3, o represents 0～7 integer, p, q are respectively identical or different, the integer of expression 0～3) and the multi-functional cyanate selected in the compound of expression and/or from its oligopolymer, select at least a kind;
As above-mentioned (C) epoxy resin, use from reaching the Resins, epoxy of (10) expression and/or contain at least a kind of Resins, epoxy selecting the silane-modified epoxy resin of alkoxyl group with following general formula (8), (9):
(and above-mentioned various middle G is the organic group of representing with following structural,
I, j, k represent 0～5 integer, R respectively independently
10, R
11, R
12, R
13The alkyl of representing hydrogen atom or carbonatoms 1～4 respectively independently).
20. laminated product, this laminated product has one deck and contains the layer of compositions of thermosetting resin more than one deck, said composition contains (A) polyimide resin and as (B) multi-functional cyanate of thermoset composition and (C) at least a kind in the epoxy resin;
As above-mentioned (A) polyimide resin, be to use at least, make at least a kind of acid dianhydride, the soluble polyimide that obtains with diamine reactant with following general formula (1) expression:
(in the formula, V represents to be selected from-O-,-CO-,-O-T-O-and-divalent group in the COO-T-OCO-group, T represents the divalent organic group).
21. a circuit substrate, this circuit substrate adopt compositions of thermosetting resin to constitute, said composition contains (A) polyimide resin and as (B) multi-functional cyanate of thermoset composition and (C) at least a kind in the epoxy resin;
As above-mentioned (A) polyimide resin, make at least with following general formula (1):
(in the formula, V represents to be selected from-O-,-CO-,-O-T-O-and-divalent group in the COO-T-OCO-group, T represents the divalent organic group)
At least a kind of acid dianhydride of expression reacts the soluble polyimide that obtains with two amines.
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|---|---|---|---|
| JP2002064203 | 2002-03-08 | ||
| JP64203/2002 | 2002-03-08 | ||
| JP2002200576 | 2002-07-09 | ||
| JP200576/2002 | 2002-07-09 | ||
| JP2002203333 | 2002-07-11 | ||
| JP203333/2002 | 2002-07-11 | ||
| JP2002321523 | 2002-11-05 | ||
| JP321523/2002 | 2002-11-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB038002221A Expired - Fee Related CN1309786C (en) | 2002-03-08 | 2003-03-06 | Thermosetting resin composition and laminates and circuit board substrates made by using same |
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| Country | Link |
|---|---|
| US (2) | US20050119381A1 (en) |
| JP (1) | JPWO2003076515A1 (en) |
| KR (1) | KR100960174B1 (en) |
| CN (1) | CN1309786C (en) |
| TW (1) | TWI290569B (en) |
| WO (1) | WO2003076515A1 (en) |
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| JP2001200157A (en) * | 2000-01-14 | 2001-07-24 | Mitsubishi Gas Chem Co Inc | Thermosetting resin composition |
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-
2003
- 2003-03-06 WO PCT/JP2003/002626 patent/WO2003076515A1/en active Application Filing
- 2003-03-06 US US10/505,727 patent/US20050119381A1/en not_active Abandoned
- 2003-03-06 KR KR1020037011647A patent/KR100960174B1/en active IP Right Grant
- 2003-03-06 JP JP2003574727A patent/JPWO2003076515A1/en active Pending
- 2003-03-06 CN CNB038002221A patent/CN1309786C/en not_active Expired - Fee Related
- 2003-03-07 TW TW092104933A patent/TWI290569B/en not_active IP Right Cessation
-
2008
- 2008-02-19 US US12/033,748 patent/US20080312383A1/en not_active Abandoned
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| CN1982371B (en) * | 2005-12-16 | 2012-03-07 | 佳能株式会社 | Resin composition, resin cured product, and liquid discharge head |
| CN100410325C (en) * | 2006-01-26 | 2008-08-13 | 广东生益科技股份有限公司 | Resin composition and its use in bonding sheet and copper clad plate |
| CN103517782A (en) * | 2011-05-25 | 2014-01-15 | 播磨化成株式会社 | Soldering paste flux and soldering paste |
| CN105026510A (en) * | 2013-01-22 | 2015-11-04 | 东丽株式会社 | Adhesive composition and adhesive sheet, and cured material and semiconductor device using same |
| CN105102221A (en) * | 2013-04-16 | 2015-11-25 | 东洋纺株式会社 | Metal foil laminate |
| CN105102221B (en) * | 2013-04-16 | 2017-06-06 | 东洋纺株式会社 | metal foil laminate |
| CN108314782A (en) * | 2017-01-16 | 2018-07-24 | 臻鼎科技股份有限公司 | The polyimide film and circuit board of resin combination and the application resin combination |
| US10428238B2 (en) | 2017-01-16 | 2019-10-01 | Zhen Ding Technology Co., Ltd. | Resin composition, polyimide film and method for manufacturing polyimide film |
| US10822522B2 (en) | 2017-01-16 | 2020-11-03 | Zhen Ding Technology Co., Ltd. | Modified polyimide compound, resin composition and polyimide film |
| CN110691805A (en) * | 2017-05-31 | 2020-01-14 | 积水化学工业株式会社 | Curable resin composition, cured product, adhesive film, cover lay film, and printed wiring board |
| CN111560171A (en) * | 2019-02-13 | 2020-08-21 | 味之素株式会社 | Resin composition |
| CN111642068A (en) * | 2020-06-10 | 2020-09-08 | 浙江福斯特新材料研究院有限公司 | RCC substrate and multi-layer laminated flexible board |
| CN114369401A (en) * | 2020-10-15 | 2022-04-19 | 味之素株式会社 | Resin composition, cured product, sheet-like laminate, resin sheet, printed wiring board, and semiconductor device |
Also Published As
| Publication number | Publication date |
|---|---|
| TW200401000A (en) | 2004-01-16 |
| TWI290569B (en) | 2007-12-01 |
| US20050119381A1 (en) | 2005-06-02 |
| JPWO2003076515A1 (en) | 2005-07-07 |
| CN1309786C (en) | 2007-04-11 |
| KR100960174B1 (en) | 2010-05-26 |
| KR20040090387A (en) | 2004-10-22 |
| US20080312383A1 (en) | 2008-12-18 |
| WO2003076515A1 (en) | 2003-09-18 |
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